JP2015200704A - Sheet with frame - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet with frame which has superior optical transparency and antireflection performance and hardly accumulates dust, and a manufacturing method of the sheet with frame at a low cost.SOLUTION: The sheet with frame includes: a light transmissive member that has a fine rugged structure of plural salients on the surface thereof, which are formed at a frequency of equal to or smaller than the wave length in a visible light region; and a frame part on the surface of the light transmissive member. In the sheet with frame, the surface of the light transmissive member having the fine rugged structure and the frame part are joined via an adhesive member. The manufacturing method of the sheet with frame includes a step to bond a first light transmissive member and a second light transmissive member by means of thermal fusion bonding so that the sheet with frame has the fine rugged structure on both sides.

Description

  The present invention relates to a framed sheet having antireflection performance.

In recent years, for the purpose of imparting antireflection properties, antifogging properties, antifouling properties, water repellency, and the like, molded bodies such as functional films having a fine concavo-convex structure on the surface have been proposed. In particular, it is known that a fine concavo-convex structure called a Moth-Eye structure exhibits excellent antireflection properties.
As a method for forming a fine concavo-convex structure on the surface of a molded body, a method for directly processing the surface of a material, a transfer method for transferring the structure using a stamper (mold) having an inverted structure corresponding to the fine concavo-convex structure, etc. The latter method is superior in terms of productivity and economy. As a method for forming an inversion structure on a stamper, an electron beam drawing method, a laser beam interference method, and the like are known. However, as a method for forming an inversion structure more easily in recent years, the surface of an aluminum substrate is anodized. The method is drawing attention.

  The functional film having the above-described fine concavo-convex structure on the surface is often provided with a fine concavo-convex structure layer on the surface, a base material, and an adhesive layer for adhering the film to the article. In some cases, adhesive residue or the like on the article when removed after use becomes a problem.

  Conventionally, for the purpose of improving the handleability of optical films, it consists of a laminate having an optical film layer and an adhesive layer, and the edges of the laminate are formed on a rough surface with fine irregularities and covered with a non-adhesive film. An optical member formed has been proposed (Patent Document 1).

  In addition, a display case has been proposed in which a transparent plate having a moth-eye effect due to a fine concavo-convex structure on the surface is covered with the display so that the display can be seen well from the outside (Patent Document 2).

JP-A-11-254550 JP 2010-48902 A

However, the optical member described in Patent Document 1 requires a process for fixing the end sides, and although troubles during transportation can be solved, handling when installing or removing the optical member on an article is possible. Sex was not considered.
The display case described in Patent Document 2 is a low-reflection transparent plate in which a reflection-reducing film is pasted on both sides of an acrylic plate, so that the interface between the reflection-reducing film and the acrylic plate exists on both sides of the acrylic plate. As a result, the light transmittance of the reflection reducing film could not be sufficiently exhibited. Furthermore, since a low reflection transparent plate is set on a forehead or a show window to form a display case, a sticking process, plate cost, etc. are required and the cost increases.

  This invention makes it a subject to provide the sheet | seat with a frame excellent in visibility and favorable handleability.

The present invention has the following aspects.
[1] A light-transmitting member having a fine concavo-convex structure composed of a plurality of convex portions formed with a period equal to or less than the wavelength of the visible light region on the surface, and a framed sheet having a frame portion on the surface of the light-transmitting member .
[2] The framed sheet according to [1], wherein the surface of the light-transmitting member having a fine uneven structure and the frame part are bonded via an adhesive member.
[3] The framed sheet according to [1] to [2], wherein the light transmissive member has a fine uneven structure on both sides.
[4] The framed sheet according to [1] to [3], which includes an adhesive layer between the first light transmissive member and the second light transmissive member.
[5] The framed sheet according to [1] to [4], wherein the frame part includes a self-adhesive member.
[6] The framed sheet according to [1] to [5], which is an ink layer on which a frame part is printed.
[7] An article provided with the framed sheet according to [1] to [6].
[8] including bonding the first light transmissive member and the second light transmissive member by heat-sealing so that the surfaces having the fine concavo-convex structures are both surfaces of the framed sheet, The manufacturing method of the sheet | seat with a frame as described in [1]-[6].
[9] including bonding the first light-transmitting member and the second light-transmitting member via an adhesive layer so that the surfaces having the respective fine concavo-convex structures are both surfaces of the framed sheet. , [1] to [6].

Since the framed sheet of the present invention has excellent antireflection performance, if the framed sheet is arranged on the viewing side of the article, reflection of light on the article can be prevented, and dust is less likely to adhere. Good visibility can be obtained. In addition, the framed sheet of the present invention has good handleability due to the presence of a frame in close contact with the sheet. Furthermore, the design can be imparted to the frame.
According to the method for manufacturing a framed sheet of the present invention, it is possible to easily manufacture a framed sheet having good visibility and excellent handleability.

It is a fragmentary sectional view showing an example of a sheet with a frame of the present invention. It is a fragmentary sectional view showing other examples of a sheet with a frame of the present invention. It is sectional drawing which shows an example of the article | item which comprises the sheet | seat with a frame of this invention in the visual recognition side. It is sectional drawing which shows an example of a light transmissive member. It is sectional drawing which shows another example of a light transmissive member. It is a block diagram which shows an example of the manufacturing apparatus of a light transmissive member.

Hereinafter, the present invention will be described in detail.
In the present specification, the surface on the side where the fine uneven structure of the film-like light transmissive member is formed is referred to as the “surface of the light transmissive member”, and the fine uneven structure of the film-like light transmissive member is The surface that is not formed is referred to as the “back surface of the light transmissive member”. The surface on the side of the framed sheet where the fine concavo-convex structure is formed is called “the surface of the framed sheet”, and the surface on the side of the framed sheet where the fine concavo-convex structure is not formed is called “the back surface of the framed sheet” "
In addition, “light transmissivity” in this specification means that light having a wavelength of 400 to 1170 nm is transmitted.
In addition, “active energy rays” in the present specification means visible light, ultraviolet rays, electron beams, plasma, heat rays (infrared rays, etc.) and the like.
In the present specification, “(meth) acrylate” is a generic term for acrylate and methacrylate, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, and “(meth) acrylonitrile” is acrylonitrile. And “(meth) acrylamide” is a generic name for acrylamide and methacrylamide.
In FIGS. 1 to 5, the scales are different for each layer in order to make each layer recognizable on the drawing.
Moreover, in FIGS. 1-5, the same code | symbol is attached | subjected to the same component and the description may be abbreviate | omitted.

<Sheet with frame>
FIG. 1 is a partial sectional view showing an example of a framed sheet according to the present invention. The framed sheet 1 of this example is a light transmissive member having a fine concavo-convex structure composed of a plurality of convex portions formed on one surface with a period equal to or less than the wavelength of the visible light region as illustrated in FIG. The frame portion 2 is bonded to one surface of the light transmissive member 20 having a fine concavo-convex structure formed of a plurality of convex portions formed at a period equal to or less than the wavelength of the visible light region on the surface of 10 or both via the adhesive member 4. Has been.
As illustrated in FIG. 1B, the frame portion 2 may be joined so as to cover both surfaces and side surfaces of the light transmissive member 10 or the light transmissive member 20. The frame portion 2 shown in FIG. 1B has a target shape on both surfaces of the light transmissive member, but may be asymmetric. Moreover, the adhesive member may be arrange | positioned in all the parts which contact | connect a light transmissive member, and may be arrange | positioned partially. Since the light-transmitting member and the frame portion can be firmly bonded, it is preferable that the area through the adhesive member is large.
In FIG. 1, the light transmissive member 10 or the light transmissive member 20 and the frame portion 2 are bonded via the adhesive member 34, but may be bonded without using the adhesive member 34 as will be described later. .
In the sheet with a frame of the present invention, the frame part may be bonded to the entire sheet edge part, or may be bonded to a part of the sheet edge part. From the viewpoint of ease of handling, it is preferable that the frame portion is bonded to the entire sheet end portion.

FIG. 2 is a partial cross-sectional view showing another example of the framed sheet of the present invention. As in FIG. 1, the light transmissive member 10 or the light transmissive member 20 and the frame portion 2 are joined via the adhesive member 4, but the spacer 6 is disposed on the side surface of the light transmissive member.
The shape, material, function and the like of the spacer 6 are not particularly limited. A shape that fills all the gaps between the light transmissive member 10 or the light transmissive member 20 and the frame portion 2 is preferable because the light transmissive member and the frame portion are more stably fixed. The spacer 6 may be a solid, a gel, or a sponge.
The spacer 6 may be an adhesive. If the spacer 6 is an adhesive, the light transmissive member 10 or the light transmissive member 20 and the frame portion 2 can be fixed in addition to the bonding by the adhesive member 4.
In FIG. 2, a mounting jig 8 is further provided. The attachment jig 8 makes it easy to attach the framed sheet to the article. For example, an adhesive, a double-sided tape, a suction cup, a magnet, a pin, etc. are mentioned. In addition, things other than the attachment jig may be provided at the position of the attachment jig 8. Examples other than the mounting jig include lighting, illuminant, insect repellent, desiccant, humidity control material, fragrance, and acoustic equipment 7.

FIG. 3 is a cross-sectional view showing an example of an article provided with the framed sheet of the present invention on the viewing side.
The article 50 is not particularly limited. The shape of the article may be one having a flat surface or one having irregularities on the surface. For example, a picture, a poster, a textile, a cutout, a writing, a photograph, a writing, a scroll, etc. are mentioned.
By disposing the framed sheet of the present invention on the surface of the article 50 on the viewing side, when the article 50 is viewed from the viewing side through the framed sheet, reflection by external light can be suppressed, and the surrounding light source Further, the article 50 can be clearly seen without the image of the person who is viewing the image being reflected.
Moreover, a backlight can be arrange | positioned on the surface which is not the visual recognition side of the goods 50, and the goods 50 can also be shown more clearly.

  As illustrated in FIG. 3A, when the framed sheet 1 is integrated with the article 50 via the adhesive member 4a, it is easy to handle as a bulletin board or a display object. The adhesive member 4a is not particularly limited, but if it is a self-adhesive member, the light transmissive member 10 or the light transmissive member 20 can be easily detached from the article 50. In addition, when the light transmissive member 20 and the article 50 are bonded via the adhesive member 4a, the light transmissive member 20 has a strong adhesive force with the article 50 due to the fine uneven structure on the surface. On the other hand, since the adhesive force between the article 50 and the adhesive member 4 a is not as strong as the adhesive force between the light transmissive member 20 and the article 50, the article 50 and the adhesive member are removed when the framed sheet 1 is peeled from the article 50. Since it is easy to peel at the interface with 4a, desorption becomes easy. Similarly, when a weakly adhesive material is used for the adhesive member 4a, the adhesive force between the light transmissive member 20 and the article 50 is increased even if the adhesive force between the article 50 and the adhesive member 4a is weakly adhesive. When the frame-equipped sheet 1 is peeled from the article 50, it is easy to peel off at the interface between the article 50 and the adhesive member 4a, and the attachment / detachment is facilitated.

As illustrated in FIG. 3B, the framed sheet 1 may be disposed so as to cover the article 50. The light transmissive member 10 or the light transmissive member 20 and the article 50 may be in contact with each other, or may be disposed with a space therebetween. The interval is not particularly limited. It may be several mm or several m.
As illustrated in FIG. 3A or 3B, when the framed sheet 1 and the article 50 are integrated, it is easy to handle as a bulletin board or a display object.
Although not illustrated, when the framed sheet 1 illustrated in FIG. 2 is arranged on the viewing side of the article 50, the framed sheet 1 and the article 50 are easily integrated by the mounting jig. For example, when a magnet is disposed as the mounting jig 8, the frame-equipped sheet 1 can be easily attached and detached by a magnetic force if a metal fitting is provided on the end surface or the back surface of the article.

(Light transmissive member)
FIG. 4 is a cross-sectional view illustrating an example of the light transmissive member 10. The light transmissive member 10 has on one surface a fine concavo-convex structure composed of a plurality of convex portions 13 formed with a period equal to or shorter than the wavelength of the visible light region. The light transmissive member 10 includes a base material 12a and a cured resin layer 11a formed on the surface of the light transmissive member 10 and having a fine concavo-convex structure including a plurality of convex portions 13 on the surface. .
The light transmissive member may have a fine concavo-convex structure on one surface like the light transmissive member 10 illustrated in FIG. 4, or a fine concavo-convex structure on both surfaces as described later. It may be.
The thickness of the light-transmitting member can be arbitrarily set, but is preferably 0.2 to 2 mm because the balance between visibility and handleability is good.

(Base material)
Examples of the material for the substrate 12a include acrylic resins, polycarbonates, polystyrene resins, polyesters, cellulose resins (such as triacetylcellulose), polyolefins, alicyclic polyolefins, and glass.
The surface of the substrate 12a may be subjected to coating or corona treatment for the purpose of improving properties such as adhesion, antistatic properties, scratch resistance, and weather resistance.

(Cured resin layer)
The cured resin layer 11a is a film made of a cured product of an active energy ray-curable resin composition, which will be described later, and has a fine concavo-convex structure made up of a plurality of convex portions 13 on the surface.

  The method for forming the fine concavo-convex structure is not particularly limited, and examples thereof include a method of directly forming on a molded body and a method of transferring from a mold having a fine concavo-convex structure (transfer method). In the case of the transfer method, the fine concavo-convex structure is preferably formed by transferring a plurality of pores of anodized alumina described later. The fine concavo-convex structure formed by transferring a plurality of pores of anodized alumina can be formed at a low cost and can have a large area.

The average interval (period) P between adjacent convex portions 13 of the fine concavo-convex structure is not more than the wavelength of the visible light region, that is, not more than 400 nm, preferably not more than 300 nm, and more preferably not more than 250 nm. When the convex portions 13 are formed by transferring a plurality of pores of the anodized alumina, it is necessary to increase the voltage in order to increase the pore interval, which makes it difficult to manufacture industrially. The average interval P is particularly preferably 200 nm or less. When the average interval P between the convex portions 13 is equal to or less than the wavelength in the visible light region, the reflectance is low and the wavelength dependency of the reflectance is small.
The average interval P between the convex portions 13 is preferably 20 nm or more, more preferably 80 nm or more, from the viewpoint of easy formation of the convex portions 13.
The average interval P between the convex portions 13 is obtained by measuring 50 intervals between the adjacent convex portions 13 (distance from the center of the convex portion 13 to the center of the adjacent convex portion 13) by electron microscope observation. Is the average.

The average height H of the protrusions 13 is preferably 100 nm or more, and more preferably 130 nm or more. When the average height H of the convex portions 13 is 100 nm or more, the reflectance is low and the wavelength dependence of the reflectance is small. In addition, sufficient adhesion between layers can be secured. The average height H of the protrusions 13 is preferably 400 nm or less, and more preferably 300 nm or less, from the viewpoint of easy formation of the protrusion structure.
The average height H of the convex portion 13 is obtained by measuring the distance between the topmost portion 13t of the convex portion 13 and the bottommost portion 13d of the concave portion existing between the convex portions 13 by observation with an electron microscope. Is the average.

0.8-5 are preferable, as for the aspect ratio (H / P) of the convex part 13, 1.2-4 are more preferable, and 1.5-3 are still more preferable. If the aspect ratio of the convex portion 13 is 0.8 or more, the reflectance is sufficiently low. When the aspect ratio of the convex portion 13 is 5 or less, the scratch resistance of the convex portion 13 is good.
Examples of the shape of the convex portion 13 include a substantially conical shape, a pyramid shape, a bell shape, and a cylindrical shape.

  FIG. 5 is a cross-sectional view showing another example of the light transmissive member. The above-described light transmissive member 10 is bonded to both surfaces of the adhesive layer 15. By having the fine concavo-convex structure on both surfaces of the light-transmitting member, it is possible to exhibit an antireflection performance that is even better than that on one surface.

(Adhesive layer)
The adhesive layer 15 is not particularly limited as long as it can adhere a light transmissive member, but is preferably light transmissive after adhesion. It is preferable that the refractive index difference with the refractive index of the base material of the light transmissive member provided with the base material and the cured resin layer having a fine concavo-convex structure is within a range of −0.05 to 0.05. If the refractive index difference between the light-transmitting base member and the base material is within the above range, when the light-transmitting member is viewed from any cured resin layer side of the light-transmitting member bonded to both surfaces of the adhesive layer However, reflection by external light can be suppressed, which is preferable.
Examples of the adhesive layer 15 include an acrylic pressure-sensitive adhesive material, a polyester-based pressure-sensitive adhesive material, and an epoxy-based pressure-sensitive adhesive material. Is preferable.
The adhesive layer may have functions such as infrared light, ultraviolet light, blue light, and light. Moreover, when making it adhere | attach, there exists a softness | flexibility and it may harden | cure after adhesion | attachment and a hard-coat agent may be sufficient.

The light transmissive member may have a configuration other than that illustrated in FIGS. 4 and 5.
The light transmissive member may be a member obtained by thermally fusing the base material of the first light transmissive member and the base material of the second light transmissive member without using an adhesive layer. If the base material of the first light transmissive member and the base material of the second light transmissive member are made of the same material, there will be no difference in refractive index, and the light transmittance and antireflection performance will be better.
The light transmissive member may be provided with a cured resin layer having a fine concavo-convex structure on both surfaces of the substrate of the light transmissive member. That is, the second cured resin layer may be formed on the surface of the substrate 12a of FIG. 4 that is not in contact with the cured resin layer 11a. With such a configuration, the number of interfaces between layers is small, and both surfaces of the light transmissive member have a fine concavo-convex structure, so that the light transmittance and the antireflection performance are extremely excellent.

The light transmissive member may be obtained by bonding the light transmissive member 20 illustrated in FIG. 5 to both surfaces of another adhesive layer. The fine concavo-convex structure on the surface of the light transmitting member may be on the entire surface of the framed sheet or may be partially present. By intentionally arranging the fine concavo-convex structure part intentionally, the appearance of the article can be freely produced.
A release agent may be applied to the surface of the cured resin layer having a fine uneven structure on the viewing side, and a light transmissive member may be further laminated. Even when the outermost light-transmitting member is damaged, by peeling the outermost light-transmitting member, another light-transmitting member that is not in contact with the outer surface becomes the outermost surface, and the light-transmitting property of the framed sheet In addition, the antireflection performance can be maintained in a good state.

(Frame part)
The shape, material, etc. of the frame part provided in the framed sheet of the present invention are not limited. The shape of the frame portion may be, for example, a shape that covers the entire end portion of the light transmissive member as described above, or a shape that is partially disposed. The material of the frame is, for example, a metal such as wood, plastic, aluminum, foamed vinyl chloride, paint, acrylic resin, maleic acid resin, rosin resin, epoxy resin, silicone resin, butyral resin, acrylic resin, acrylic Block copolymers, anionic azo dyes, dyes such as phthalocyanine; pigments such as carbon black and organic pigments. The size of the frame can be appropriately set as necessary. For example, in the case of a display object such as a content panel, the width may be 2 to 5 cm and the entire end may be covered.
As illustrated in FIG. 1 and FIG. 2, if the light-transmitting member and the frame portion are joined via the adhesive member, the strength as a framed sheet is increased and the handleability is also improved. Moreover, you may print on a light transmissive member by using said resin etc. as a frame part. Printing may be on the viewing side of the light transmissive member or on the article side. If a printed frame is provided on the article side, the printing itself can be seen clearly. The frame portion can also have design properties.

(Adhesive material)
In the sheet with a frame of the present invention, the surface of the light transmissive member having a fine uneven structure and the frame part may be bonded via an adhesive member. The adhesive member is not particularly limited, but the light-transmitting member and the adhesive member have good adhesion due to the fine uneven structure on the surface of the light-transmitting member. can do.

<Article>
The article provided with the framed sheet of the present invention has improved visibility of the article. The arrangement of the article and the framed sheet is not particularly limited, and the article and the framed sheet may be in contact with each other or may have a gap. A framed sheet may be disposed on the entire surface of the article, or may be disposed on a part of the article.

<Method for producing light transmissive member>
The light transmissive member 10 is manufactured as follows using, for example, a manufacturing apparatus shown in FIG.
A surface of a roll-shaped mold 30 on which anodized alumina having a plurality of pores (not shown) is formed, and a strip-shaped base material 12 that moves along the surface of the mold 30 in synchronization with the rotation of the mold 30. The active energy ray-curable resin composition is supplied from the tank 32 between the surface and the surface.

  The base material 12 and the active energy ray curable resin composition are nipped between the mold 30 and the nip roll 36 whose nip pressure is adjusted by the pneumatic cylinder 34, and the active energy ray curable resin composition is niped. And the mold 30 are uniformly distributed, and at the same time, the pores of the mold 30 are filled.

The active energy ray curable resin composition is sandwiched between the mold 30 and the base material 12, and the active energy ray irradiation device 38 installed below the mold 30 is used to start the tank from the base material 12 side. A plurality of pores on the surface of the mold 30 are transferred by irradiating the active energy ray-curable resin composition supplied from 32 with active energy rays and curing the active energy ray-curable resin composition. A cured resin layer 16 having a fine concavo-convex structure made up of a plurality of convex portions (not shown) on the surface is formed.
The light transmissive member 10 is obtained by peeling the sheet composed of the cured resin layer 11 and the substrate 12 having the cured resin layer 11 formed on the surface by the peeling roll 40.

As the active energy ray irradiation device 38, a high-pressure mercury lamp, a metal halide lamp, a fusion UV, or the like is preferable. The integrated light quantity is preferably 100 to 10,000 mJ / cm ² .

  As a method for producing a light transmissive member provided in the framed sheet of the present invention, in addition to the above method, for example, the mold is peeled after transferring the fine uneven shape of the mold to the curable composition, and then the active energy ray And a method of curing the curable composition by irradiation. From the viewpoint of the transferability of the fine concavo-convex structure and the degree of freedom of the surface composition, a curable resin composition is disposed between the surface of the mold having the fine concavo-convex structure on the surface and the substrate, and the curable composition is A method of peeling the mold after curing is particularly preferable. This method is particularly suitable when using a belt-shaped or roll-shaped mold capable of continuous production, and is a method with excellent productivity.

(Active energy ray-curable composition)
The material of the cured resin layer constituting the fine concavo-convex structure provided on the surface of the framed sheet of the present invention is not limited, but a cured curable resin composition is preferable because it is easy to produce, and the active energy ray curable resin composition Is particularly preferred. Moreover, what has a light transmittance after hardening is preferable. The active energy ray-curable resin composition contains a polymerizable compound and a polymerization initiator.
Examples of the polymerizable compound include monomers, oligomers, and reactive polymers having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule.
The active energy ray-curable resin composition may contain a non-reactive polymer and an active energy ray sol-gel reactive composition.

Examples of the monomer having a radical polymerizable bond include a monofunctional monomer and a polyfunctional monomer.
Monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, alkyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, Phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl ( )) (Meth) acrylate derivatives such as acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate; (meth) acrylic acid, (meth) acrylonitrile; styrene, α -Styrene derivatives such as methylstyrene; (meth) acrylamide derivatives such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide and the like.
These may be used alone or in combination of two or more.

As polyfunctional monomers, ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, polybutylene glycol di ( (Meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- ( 3- (Me ) Acryloxy-2-hydroxypropoxy) phenyl) propane, 1,2-bis (3- (meth) acryloxy-2-hydroxypropoxy) ethane, 1,4-bis (3- (meth) acryloxy-2-hydroxypropoxy) Butane, dimethyloltricyclodecane di (meth) acrylate, ethylene oxide adduct di (meth) acrylate of bisphenol A, propylene oxide adduct di (meth) acrylate of bisphenol A, neopentyl glycol di (meth) acrylate of hydroxypivalate , Divinylbenzene, methylenebisacrylamide and other bifunctional monomers; pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide Trifunctional monomers such as tri (meth) acrylate, trimethylolpropane propylene oxide modified triacrylate, trimethylolpropane ethylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate; condensation of succinic acid / trimethylolethane / acrylic acid Tetrafunctional or higher monomer such as reaction mixture, dipentaerystol hexa (meth) acrylate, dipentaerystol penta (meth) acrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethanetetra (meth) acrylate; bifunctional or higher urethane Examples thereof include acrylates and bifunctional or higher polyester acrylates.
These may be used alone or in combination of two or more.

  Examples of the monomer having a cationic polymerizable bond include monomers having an epoxy group, an oxetanyl group, an oxazolyl group, a vinyloxy group, and the like, and a monomer having an epoxy group is particularly preferable.

  Examples of oligomers or reactive polymers include unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols; polyester (meth) acrylates, polyether (meth) acrylates, polyol (meth) acrylates, epoxy (meth) Examples thereof include acrylates, urethane (meth) acrylates, cationic polymerization type epoxy compounds, homopolymers of the above-described monomers having a radical polymerizable bond in the side chain, and copolymerized polymers.

Examples of non-reactive polymers include acrylic resins, styrene resins, polyurethanes, cellulose resins, polyvinyl butyral, polyesters, thermoplastic elastomers, and the like.
Examples of the active energy ray sol-gel reactive composition include alkoxysilane compounds and alkyl silicate compounds.

As an alkoxysilane compound, the compound of following formula (1) is mentioned.
R ¹¹ _x Si (OR ¹² ) _y (1)
^However, R ^{11, R 12} each represent an alkyl group having 1 to 10 carbon atoms, x, y represents an integer satisfying the relation of x + y = 4.

  Examples of the alkoxysilane compound include tetramethoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-t-butoxysilane, methyltriethoxysilane, Examples include methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, trimethylpropoxysilane, and trimethylbutoxysilane.

Examples of the alkyl silicate compound include a compound of the following formula (2).
R ²¹ O [Si (OR ²³ ) (OR ²⁴ ) O] _z R ²² (2)
^However, R 21 ^{to R 24} each represent an alkyl group having 1 to 5 carbon atoms, z is an integer of 3 to 20.

  Examples of the alkyl silicate compound include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, n-pentyl silicate, acetyl silicate and the like.

When utilizing a photocuring reaction, examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxy. Acetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropane- Carbonyl compounds such as 1-one; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyl Examples include diethoxyphosphine oxide.
These may be used alone or in combination of two or more.

When using an electron beam curing reaction, examples of the polymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t- Thioxanthone such as butylanthraquinone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl Dimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholy Phenyl) -butanone and other acetophenones; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)- Acylphosphine oxides such as 2,4,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; methylbenzoylformate, 1,7-bisacridinylheptane, 9-phenyl Examples include acridine.
These may be used alone or in combination of two or more.

  When utilizing a thermosetting reaction, examples of the thermal polymerization initiator include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxy octoate, organic peroxides such as t-butylperoxybenzoate and lauroyl peroxide; azo compounds such as azobisisobutyronitrile; N, N-dimethylaniline, N, N-dimethyl-p- Examples thereof include a redox polymerization initiator combined with an amine such as toluidine.

The active energy ray-curable resin composition may contain an antistatic agent, a release agent, an additive such as a fluorine compound for improving the antifouling property, fine particles, and a small amount of a solvent, if necessary.
Moreover, it is preferable that the hardened | cured material of an active energy ray curable resin composition is water-repellent from an antifouling point. Moreover, it is preferable that it is hydrophilic from a viewpoint of anti-fogging property. It can select suitably as needed.

(Water repellent material)
When the surface of the fine concavo-convex structure is required to have water repellency (specifically, a water contact angle of 135 ° or more), as an active energy ray-curable resin composition capable of forming a water repellant material, It is preferable to use a composition containing a fluorine-containing compound or a silicone-based compound. A compound having a long chain alkyl group may be used.

Fluorine-containing compounds:
As the fluorine-containing compound, a compound having a fluoroalkyl group represented by the following formula (3) is preferable.
_{- (CF 2) n -X ···} (3)
However, X represents a fluorine atom or a hydrogen atom, n represents an integer greater than or equal to 1, 1-20 are preferable, 3-10 are more preferable, and 4-8 are especially preferable.

  Examples of the fluorine-containing compound include a fluorine-containing monomer, a fluorine-containing silane compound, a fluorine-containing surfactant, and a fluorine-containing polymer.

Examples of the fluorine-containing monomer include a fluoroalkyl group-substituted vinyl monomer and a fluoroalkyl group-substituted ring-opening polymerizable monomer.
Examples of the fluoroalkyl group-substituted vinyl monomer include fluoroalkyl group-substituted (meth) acrylates, fluoroalkyl group-substituted (meth) acrylamides, fluoroalkyl group-substituted vinyl ethers, and fluoroalkyl group-substituted styrenes.

  Examples of the fluoroalkyl group-substituted ring-opening polymerizable monomer include fluoroalkyl group-substituted epoxy compounds, fluoroalkyl group-substituted oxetane compounds, and fluoroalkyl group-substituted oxazoline compounds.

As the fluorine-containing monomer, a fluoroalkyl group-substituted (meth) acrylate is preferable, and a compound of the following formula (4) is particularly preferable.
^{_{CH 2 = C (R 41)}} C (O) O- (CH 2) m - (CF 2) n -X ··· (4)
However, R ^<41 > represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a fluorine atom, m represents the integer of 1-6, 1-3 are preferable, 1 or 2 is more preferable, n Represents an integer of 1 to 20, preferably 3 to 10, and more preferably 4 to 8.

As the fluorine-containing silane compound, a fluoroalkyl group-substituted silane compound is preferable, and a compound of the following formula (5) is particularly preferable.
(R ^f ) _a R ⁵¹ _b SiY _c (5)

^Rf represents a C1-C20 fluorine-substituted alkyl group which may contain one or more ether bonds or ester bonds. Examples of R ^f include 3,3,3-trifluoropropyl group, tridecafluoro-1,1,2,2-tetrahydrooctyl group, 3-trifluoromethoxypropyl group, and 3-trifluoroacetoxypropyl group. It is done.

R ⁵¹ represents an alkyl group having 1 to 10 carbon atoms. Examples of R ⁵¹ include a methyl group, an ethyl group, and a cyclohexyl group.

Y represents a hydroxyl group or a hydrolyzable group.
Examples of the hydrolyzable group include an alkoxy group, a halogen atom, and R ⁵² C (O) O (wherein R ⁵² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).
Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, Examples include octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, and the like.
Examples of the halogen atom include Cl, Br, I and the like.
Examples of R ⁵² C (O) O include CH ₃ C (O) O, C ₂ H ₅ C (O) O, and the like.

  a, b, and c are integers satisfying a + b + c = 4 and satisfying a ≧ 1, c ≧ 1, and preferably a = 1, b = 0, and c = 3.

  Fluorine-containing silanes and pulling agents include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriacetoxysilane, dimethyl-3,3,3-trifluoropropylmethoxysilane, Examples include decafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane.

  Examples of the fluorine-containing surfactant include a fluoroalkyl group-containing anionic surfactant and a fluoroalkyl group-containing cationic surfactant.

The fluoroalkyl group-containing anionic surfactants include fluoroalkyl carboxylic acid or a metal salt of 2 to 10 carbon atoms, disodium perfluorooctane sulfonyl glutamic acid, 3- [omega - fluoroalkyl _(C 6 ~C ₁₁₎ oxy ] -1-alkyl _(C 3 _{~C 4)} sulfonate, sodium 3- [omega - fluoroalkanoyl _{(C 6 ~C} 8) -N- ethylamino] -1-sodium sulfonic acid, fluoroalkyl _{(C 11} ~ C ₂₀₎ carboxylic acids or metal salts thereof, perfluoroalkyl carboxylic acids _(C 7 _{~C 13)} or metal salts thereof, perfluoroalkyl _(C 4 _{~C 12)} sulfonic acid or metal salts thereof, diethanol perfluorooctane sulfonic acid Ami N-propyl-N- (2-hydroxyethyl) Over perfluorooctane sulfonamide, perfluoroalkyl _(C 6 _{~C 10)} sulfonamide propyl trimethyl ammonium salts, perfluoroalkyl _{(C 6 ~C} 10) -N- ethylsulfonyl glycine salts, monoperfluoroalkyl _(C 6 -C ₁₆ ) Ethyl phosphate ester and the like.

Examples of the fluoroalkyl group-containing cationic surfactant include aliphatic quaternary compounds such as fluoroalkyl group-containing aliphatic primary, secondary or tertiary amine acids, and perfluoroalkyl (C ₆ -C ₁₀ ) sulfonamidopropyltrimethylammonium salts. Examples thereof include ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.

  Fluorine-containing polymers include polymers of fluoroalkyl group-containing monomers, copolymers of fluoroalkyl group-containing monomers and poly (oxyalkylene) group-containing monomers, and copolymers of fluoroalkyl group-containing monomers and crosslinking reactive group-containing monomers. A polymer etc. are mentioned. The fluorine-containing polymer may be a copolymer with another copolymerizable monomer.

As the fluorine-containing polymer, a copolymer of a fluoroalkyl group-containing monomer and a poly (oxyalkylene) group-containing monomer is preferable. As the poly (oxyalkylene) group, a group represented by the following formula (6) is preferable.
− (OR ⁶¹ ) _p − (6)
^{However, R 61} represents an alkylene group having 2 to 4 carbon atoms, p is an integer of 2 or more.
Examples of R ⁶¹ include —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ —, —CH (CH ₃ ) CH (CH ₃ ) —, and the like.

The poly (oxyalkylene) group may be composed of the same oxyalkylene unit (OR ⁶¹ ) or may be composed of two or more oxyalkylene units (OR ⁶¹ ). The arrangement of two or more oxyalkylene units (OR ⁶¹ ) may be a block or random.

Silicone compounds:
Examples of the silicone compound include (meth) acrylic acid-modified silicone, silicone resin, silicone silane, and a pulling agent.
Examples of the (meth) acrylic acid-modified silicone include silicone (meth) acrylates such as X-22-1602 (manufactured by Shin-Etsu Chemical Co., Ltd.), UV-3570 (manufactured by Big Chemie), OPTOOL DAC, OPTOOL DSX (manufactured by Daikin Industries). Etc.

Compounds having a long chain alkyl group:
Examples of the compound having a long chain alkyl group include octyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate. The two isocyanate groups of isocyanuric acid may be a compound in which the ends are sealed with (meth) acryloyl groups and an alkyl group having 8 or more carbon atoms is introduced into the remaining one.

(Hydrophilic material)
When hydrophilicity (specifically, the water contact angle is 30 ° or less) is required on the surface of the fine concavo-convex structure, as an active energy ray-curable resin composition capable of forming a hydrophilic material, It is preferable to use a composition containing a polyfunctional (meth) acrylate having 4 or more functions, a hydrophilic (meth) acrylate having 2 or more functions, and a monofunctional monomer as necessary.

Examples of tetrafunctional or higher polyfunctional (meth) acrylates include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, succinic acid / trimethylolethane / acrylic acid molar mixture 1: 2: 4 condensation reaction mixture, urethane acrylates (manufactured by Daicel-Cytec: EBECRYL220, EBECRYL1290K, EBECRYL1290K, EBECRYL5129, EBECRYL8210, EBECRYL 8301, KRM 8200), polyether acrylates (manufactured by Daicel-Cytec: EBEC) YL81), modified epoxy acrylates (manufactured by Daicel-Cytec: EBECRYL3416), polyester acrylates (manufactured by Daicel-Cytech: EBECRYL450, EBECRYL657, EBECRYL800, EBECRYL810, EBECRYL8111, EBECRYL81L, EBECRYL81L It is done. These may be used alone or in combination of two or more.
The polyfunctional (meth) acrylate having 4 or more functional groups is more preferably a polyfunctional (meth) acrylate having 5 or more functional groups. It is particularly preferable to use an ethoxy-modified compound.

Long-chain polyethylene such as Aronix M-240, Aronix M260 (manufactured by Toagosei Co., Ltd.), NK ester AT-20E, NK ester ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.) Examples thereof include polyfunctional acrylates having glycol and polyethylene glycol dimethacrylate. These may be used alone or in combination of two or more.
In the polyethylene glycol dimethacrylate, the total of the average repeating units of the polyethylene glycol chain present in one molecule is preferably 6 to 40, more preferably 9 to 30, and particularly preferably 12 to 20. If the average repeating unit of the polyethylene glycol chain is 6 or more, the hydrophilicity is sufficient and the antifouling property is improved. When the average repeating unit of the polyethylene glycol chain is 40 or less, the compatibility with a polyfunctional (meth) acrylate having 4 or more functionalities is improved, and the active energy ray-curable resin composition is hardly separated.

As the monofunctional monomer, a hydrophilic monofunctional monomer is preferable.
Examples of the hydrophilic monofunctional monomer include monofunctional (meth) acrylate having a polyethylene glycol chain in the ester group such as M-20G, M-90G, M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.), hydroxyalkyl (meth) acrylate, etc. And cationic monomers such as monofunctional (meth) acrylates having a hydroxyl group in the ester group, monofunctional acrylamides, methacrylamidopropyltrimethylammonium methyl sulfate, and methacryloyloxyethyltrimethylammonium methyl sulfate.
Moreover, as a monofunctional monomer, you may use viscosity modifiers, such as acryloyl morpholine and vinyl pyrrolidone, adhesive improvement agents, such as acryloyl isocyanate which improves the adhesiveness to a base material, etc.

  The monofunctional monomer may be blended in the active energy ray-curable resin composition as a polymer having a low polymerization degree obtained by (co) polymerizing one kind or two or more kinds. As a polymer having a low degree of polymerization, 40/60 of monofunctional (meth) acrylates having a polyethylene glycol chain in an ester group such as M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.) and methacrylamide propyltrimethylammonium methyl sulfate. Copolymer oligomer (MRC Unitech Co., Ltd., MG polymer) and the like can be mentioned.

<Method for producing sheet with frame>
In the first method for producing a framed sheet according to the present invention, the first light-transmitting member and the second light-transmitting member are formed such that the surfaces having the respective fine concavo-convex structures are both surfaces of the framed sheet. Including bonding by heat fusion.
As a method of heat-sealing, the first light transmitting member and the second light transmitting member are heated to a glass transition temperature or higher, and then the first light transmitting member is heated. The method of crimping | bonding the base material of a member and the base material of a 2nd light transmissive member is mentioned. Thereafter, the frame is appropriately arranged.
The base material of the first light transmissive member and the base material of the second light transmissive member may be the same material or different materials. Is preferable. Moreover, since it can adhere | attach without a joining interface, light transmittance and antireflection performance become favorable and are preferable.

In the second method for producing a framed sheet according to the present invention, the first light-transmitting member and the second light-transmitting member are formed such that the surfaces having the fine concavo-convex structures are both surfaces of the framed sheet. And adhering via an adhesive layer.
The adhesive layer used is as described above. The method for laminating each member and layer is not particularly limited, and examples thereof include a method in which an adhesive layer is subsequently disposed after the first light transmissive member is molded and the second light transmissive member is further adhered. Thereafter, the frame is appropriately arranged.

<Effect>
In the article provided with the frame-equipped sheet and the frame-equipped sheet according to the present invention described above, the effect of improving visibility due to excellent light transmission and antireflection performance can be obtained. Moreover, the adhesion between the light-transmitting member and the frame portion is strong, and the handleability is excellent. Furthermore, by having a fine concavo-convex structure on the surface, dust hardly adheres and the visibility of the article can be maintained well over a long period of time.
In the method for manufacturing a framed sheet according to the present invention, the light transmissive member is used as it is, or a plurality of the light transmissive members are joined to each other. be able to.

DESCRIPTION OF SYMBOLS 1 Sheet | seat with a frame 2 Frame part 4, 4a Adhesive member 6 Spacer 8 Mounting jig 10, 20 Light transmissive member 11, 11a, 11b Cured resin layer 12, 12a, 12b Base material 13 Convex part 13t Convex part 13d Concave part Bottom layer 15 adhesive layer 30 mold 32 tank 34 pneumatic cylinder 36 nip roll 38 active energy ray irradiation apparatus 40 peeling roll 50 article

Claims (9)

  A light-transmitting member having a fine concavo-convex structure composed of a plurality of convex portions formed with a period equal to or less than a wavelength of a visible light region on the surface, and a frame-equipped sheet having a frame portion on the surface of the light-transmitting member.   The sheet | seat with a frame of Claim 1 or 2 with which the surface and the frame part which have the fine concavo-convex structure of a light-transmitting member are joined via the adhesion member.   The frame-equipped sheet according to claim 1, wherein the light transmissive member has a fine uneven structure on both sides.   The framed sheet according to claim 1, further comprising an adhesive layer between the first light transmissive member and the second light transmissive member.   The sheet | seat with a frame of Claims 1-4 in which a frame part contains a self-adhesive member.   The framed sheet according to claim 1, wherein the frame part is an ink layer printed.   An article comprising the framed sheet according to claim 1.   The first light-transmitting member and the second light-transmitting member are bonded by heat fusion so that the surfaces having the respective fine concavo-convex structures are both surfaces of the framed sheet. The manufacturing method of the sheet | seat with a frame of -6. The first light-transmitting member and the second light-transmitting member are bonded via an adhesive layer such that the surfaces having the respective fine relief structures are both surfaces of the framed sheet. The manufacturing method of the sheet | seat with a frame of 1-6.