JP2018101016A - Functional film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a functional film which can make a protruding part less stand out gradually, the protrude part being generated by water used for attaching a resin layer and an adhesive layer together by water.SOLUTION: The present invention relates to a functional film having a resin layer being in contact with an adhesive layer when is used. The water absorption rate of the resin layer is not smaller than 2.0% by weight.SELECTED DRAWING: Figure 5

Description

  The present invention relates to a functional film.

  In recent years, various window films have been widely used. For example, there are a film that absorbs sunlight and a film that reflects sunlight as a glass scattering prevention film, a security film, or a window film that shields sunlight (see, for example, Patent Document 1).

  Such a film is usually used by being attached to a window glass through an adhesive. However, when the adhesive layer is directly attached to the window glass, bubbles may be generated or wrinkles may occur, and position correction after bonding is difficult.

Therefore, a so-called water sticking method is often used. Water sticking is the following method.
Water is applied to the glass surface in advance, a film with an adhesive layer is bonded to the glass surface on which water has been applied, and then water is driven off by rubbing the film surface with a squeegee. Furthermore, by leaving it for several hours to several days, water evaporates and the adhesion between the glass and the film is completed.
According to this method, generation of bubbles and wrinkles can be suppressed, and position correction after bonding can be performed. However, when the water sticking method is used, when the film surface is squeezed with a squeegee, the water cannot be driven out partially, and the remaining water forms a convex part, and the appearance (for example, transmitted image definition) ) Was reduced.

JP 2016-24294 A

  This invention makes it a subject to achieve the following objectives. That is, an object of the present invention is to provide a functional film capable of making a convex portion generated by water when a resin layer and an adhesive layer are laminated in contact with each other and water-applied are made inconspicuous over time.

Means for solving the above problems are as follows. That is,
<1> A functional film having a resin layer used in contact with an adhesive layer,
The functional film is characterized in that the water absorption of the resin layer is 2.0% by mass or more.
<2> The functional film according to <1>, wherein the water absorption rate of the resin layer is 5.0% by mass or more.
<3> The functional film according to any one of <1> to <2>, wherein the water absorption of the resin layer is 10% by mass or more.
<4> The functional film according to any one of <1> to <3>, wherein the resin layer has an inorganic layer on a surface opposite to the adhesive layer side.
<5> The functional film according to <4>, wherein the inorganic layer has irregularities.
<6> a first optical layer having an uneven surface;
The inorganic layer disposed on the uneven surface of the first optical layer;
A second optical layer having another uneven surface on the inorganic layer side and disposed so that the unevenness on the other uneven surface is buried;
Have
The functional film according to any one of <4> to <5>, wherein the second optical layer is the resin layer.
<7> The functional film according to any one of <1> to <6>, wherein the resin layer is a cured product of a photocurable resin composition.
<8> The functional film according to <7>, wherein the photocurable resin composition contains a polyfunctional (meth) acrylate monomer and a monofunctional (meth) acrylate compound.
<9> The functional film according to <8>, wherein the monofunctional (meth) acrylate compound contains acryloylmorpholine.

  ADVANTAGE OF THE INVENTION According to this invention, the functional film which can make the convex part produced with the water at the time of laminating | contacting and laminating | stacking by adhering a resin layer and an adhesion layer inconspicuously can be provided.

FIG. 1 is a cross-sectional view of an example of a functional film according to an embodiment of the present invention. FIG. 2 is a cross-sectional view of a state in which an adhesive layer is laminated on the resin layer of the functional film of FIG. FIG. 3 is a cross-sectional view of an example of a functional film according to another embodiment of the present invention. 4 is a cross-sectional view showing a state in which an adhesive layer is laminated on the resin layer of the functional film of FIG. FIG. 5 is a cross-sectional view of an example of a functional film according to another embodiment of the present invention. 6 is a cross-sectional view of a state in which an adhesive layer is laminated on the resin layer of the functional film of FIG. FIG. 7 is a diagram for explaining the minimum value of the thickness of the second optical layer. FIG. 8 is a perspective view showing the relationship between incident light incident on a functional film having wavelength selective reflectivity and reflected light reflected by the functional film. FIG. 9A is a perspective view showing an example of the shape of a structure formed in the first optical layer. FIG. 9B is a partial cross-sectional view illustrating a configuration example of a functional film including the first optical layer in which the structure illustrated in FIG. 9A is formed. FIG. 10A is a plan view illustrating a configuration example of the first optical layer in the functional film according to the embodiment of the present invention. 10B is a cross-sectional view of the first optical layer shown in FIG. 10A taken along line BB. FIG. 11A is a process diagram for explaining an example of a method for producing a functional film according to an embodiment of the present invention (No. 1). FIG. 11B is a process diagram for explaining an example of a method for producing a functional film according to an embodiment of the present invention (No. 2). FIG. 11C is a process diagram for explaining an example of a method for producing a functional film according to an embodiment of the present invention (No. 3). FIG. 12A is a process diagram for describing an example of a method for producing a functional film according to an embodiment of the present invention (No. 4). FIG. 12: B is process drawing for demonstrating an example of the manufacturing method of the functional film which concerns on one Embodiment of this invention (the 5). FIG. 12C is a process diagram for explaining an example of a method for producing a functional film according to an embodiment of the present invention (No. 6). FIG. 13A is a process diagram for explaining an example of a method for producing a functional film according to an embodiment of the present invention (No. 7). FIG. 13: B is process drawing for demonstrating an example of the manufacturing method of the functional film which concerns on one Embodiment of this invention (the 8). FIG. 13C is a process diagram for describing an example of a method for producing a functional film according to an embodiment of the present invention (No. 9). FIG. 13D is a process diagram for describing an example of a method for producing a functional film according to an embodiment of the present invention (No. 10).

In the present specification, “(meth) acrylate” means one or two selected from acrylate and methacrylate.
In this specification, “monofunctional (meth) acrylate” means “(meth) acrylate having one functional group”, and “multifunctional (meth) acrylate” means “a plurality of functional groups. It means “(meth) acrylate”.

(Functional film)
The functional film of this invention has a resin layer at least, and also has another member as needed.
The water absorption rate of the resin layer is 2.0% by mass or more.

In the functional film, the present inventors have laminated the resin layer and the adhesive layer in contact with each other, and when the adhesive layer is attached to the external support by water application, the water remaining between the adhesive layer and the external support is obtained. It has been found that there is a problem of causing convex portions.
Therefore, the present inventors have intensively studied to solve the above problems. Therefore, by controlling the water absorption of the resin layer, even if partially remaining water forms a convex portion, the appearance (for example, transmitted image definition) is restored over time, and there is no practical problem. As a result, the present invention has been completed.

Water sticking is a sticking method that can be re-attached, and is effective in preventing air bubbles from remaining on the adhesive surface and preventing uneven sticking. Various functional films can be smoothed through an adhesive layer. This is a method usually used when affixing to a surface (for example, glass).
In the water application, for example, an appropriate amount of a coating liquid (for example, water) is applied to an adhesive layer or glass as an external support, and then the adhesive layer is applied to the external support. At that time, by sticking the coating liquid while extruding it with a squeegee or the like, it is possible to stick without leaving bubbles and uneven sticking, and the coating liquid is discharged from between the adhesive layer and the external support. However, it is not completely discharged, and the coating liquid slightly remains between the adhesive layer and the external support and evaporates over a long time. However, the remaining water may cause a convex portion. When the generated convex part is conspicuous, the appearance is deteriorated.
In addition, although a coating liquid is water normally, in order to improve workability | operativity, a surfactant may be contained.

FIG. 1 is a cross-sectional view of an example of a functional film according to an embodiment of the present invention.
The functional film in FIG. 1 is a so-called scattering prevention / security film.
In FIG. 1, the functional film 11 includes a resin layer 3 and a first base material 4. As shown in FIG. 2, the functional film 11 is used with the adhesive layer 5 attached to the surface of the resin layer 3 opposite to the first base material 4 side. In addition, what adhered the adhesion layer 5 to the surface on the opposite side to the 1st base material 4 side in the resin layer 3 is also one Embodiment of a functional film.

FIG. 3 is a cross-sectional view of an example of a functional film according to another embodiment of the present invention.
FIG. 3 shows a so-called thermal barrier film.
In FIG. 3, the functional film 11 includes a resin layer 3, an inorganic layer 1, and a first base material 4. As shown in FIG. 4, the functional film 11 is used by attaching the adhesive layer 5 to the surface of the resin layer 3 opposite to the inorganic layer 1 side. In addition, what adhered the adhesion layer 5 to the surface on the opposite side to the inorganic layer 1 side in the resin layer 3 is also one Embodiment of a functional film.

<Resin layer>
The water absorption rate of the resin layer is 2.0% by mass or more, preferably 5.0% by mass or more, and more preferably 10% by mass or more. When the water absorption is 2.0% by mass or less, the generated convex portion remains even with lapse of time, the appearance is deteriorated, and there is a problem in use. In particular, in a functional film that exhibits optical properties, the optical properties are lowered. When the water absorption is 10% by mass or more, the convex portions that have occurred disappear in a short time (about 72 hours) after water application, and the appearance is improved.
The upper limit value of the water absorption rate is not particularly limited and may be appropriately selected depending on the purpose. However, if the water absorption rate is too large, a dimensional change associated with swelling occurs, so the water absorption rate is 50% by mass. The following is preferable, and 30% by mass or less is more preferable.

The water absorption rate of the resin layer can be determined by the following method based on, for example, JIS K 7209: 2000.
The resin layer is isolated, the mass (M ₀ ) is measured, and the resin layer is immersed in water at 25 ° C. for 24 hours. Thereafter, the water on the surface is sufficiently wiped off, and the mass (M ₂₄ ) is measured. The water absorption rate (mass%) is obtained by the following formula.
Water absorption (mass%) = (M ₂₄ −M ₀ ) / M ₀

  The resin layer is, for example, a cured product of a photocurable resin composition.

  There is no restriction | limiting in particular as a method of adjusting the water absorption rate in the said resin layer, According to the objective, it can select suitably, For example, the said resin layer is comprised with the hardened | cured material of the said photocurable resin composition. In this case, a method of determining the composition of the photocurable resin composition in consideration of the functional group amount, the number of functional groups, the blending amount, water solubility, water insolubility, and the like of the constituent components of the photocurable resin composition can be mentioned. For example, in the photocurable resin composition, the water absorption can be increased by using a water-soluble monofunctional (meth) acrylate compound or a water-soluble polyfunctional (meth) acrylate monomer. In that case, it is preferable that the resin layer has a cross-linked structure in terms of preventing elution of the resin layer by water. Further, if the crosslinking component is increased in the photocurable resin composition, the water absorption rate is decreased, the tensile elongation at break of the functional film is further decreased, and it is incompatible with the “glass scattering prevention film” defined in JIS-A5759. Therefore, the amount of the crosslinking component (for example, polyfunctional (meth) acrylate monomer) used is appropriately selected.

  When the resin layer is a flat layer, the average thickness of the resin layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 μm or more and 1,000 μm or less, and preferably 10 μm or more and 100 μm. The following is more preferable.

<< Photocurable resin composition >>
The photocurable resin composition contains at least a photoradical generator, preferably contains a radical curable material, and further contains other components as necessary.

<<< Radically curable material >>>
Examples of the radical curable material include monofunctional (meth) acrylate compounds, polyfunctional (meth) acrylate monomers, and phosphate group-containing acrylates.

  The first optical layer and the second optical layer, which will be described later, are composed of, for example, cured products of different photocurable resin compositions, but from the viewpoint of refractive index, the base resin (that is, bifunctional urethane (meth) acrylate) And monofunctional (meth) acrylate compounds) are preferably the same.

-Monofunctional (meth) acrylate compound-
The monofunctional (meth) acrylate compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alicyclic monofunctional acrylate monomer, a monofunctional acrylate monomer having a nitrogen-containing heterocycle, and a straight chain. And monofunctional acrylate monomers having an alkylene oxide chain, and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, in terms of hardness adjustment, monofunctional acrylate monomers having a cyclic structure such as alicyclic monofunctional acrylate monomers and monofunctional acrylate monomers having nitrogen-containing heterocycles, in particular, glass transition temperature Tg of 80 ° C. or higher Monofunctional acrylate monomers having the following cyclic structure are preferred.

-Alicyclic monofunctional acrylate monomer-
The alicyclic monofunctional acrylate monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include isobornyl acrylate (glass transition temperature Tg: 97 ° C.), dicyclopentenyl (meth) acrylate. (Glass transition temperature Tg: 120 ° C.), dicyclopentanyl acrylate (glass transition temperature Tg: 120 ° C.), and the like. These may be used individually by 1 type and may use 2 or more types together.

--Monofunctional acrylate monomer having nitrogen-containing heterocycle--
The monofunctional acrylate monomer having a nitrogen-containing heterocycle is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acryloylmorpholine, isopropylacrylamide, hydroxyethylacrylamide, N-acryloyloxyethylhexahydrophthalimide And pentamethylpiperidyl methacrylate. These may be used individually by 1 type and may use 2 or more types together.
Among these, acryloylmorpholine (glass transition temperature Tg: 145 ° C.) is preferable.

--Linear monofunctional acrylate monomer--
There is no restriction | limiting in particular as said linear monofunctional acrylate monomer, According to the objective, it can select suitably, For example, n-octyl acrylate (glass transition temperature Tg: -65 degreeC), stearyl acrylate (glass transition temperature) Tg: 30 ° C.) and lauryl acrylate (glass transition temperature Tg: 15 ° C.). These may be used individually by 1 type and may use 2 or more types together.

--Acrylate monomer having a hydroxyl group--
There is no restriction | limiting in particular as an acrylate monomer which has the said hydroxyl group, According to the objective, it can select suitably, For example, 1, 4- cyclohexane dimethanol monoacrylate (glass transition temperature Tg: 18 degreeC), 4-hydroxybutyl Examples thereof include acrylate, phenyl glycidyl ether acrylate (glass transition temperature Tg: −32 ° C.), 2-hydroxypropyl acrylate (glass transition temperature Tg: −7 ° C.), and the like. These may be used individually by 1 type and may use 2 or more types together.

--Monofunctional acrylate monomer having an alkylene oxide chain--
The monofunctional acrylate monomer having an alkylene oxide chain is not particularly limited and may be appropriately selected depending on the intended purpose. For example, phenoxyethyl acrylate (glass transition temperature Tg: −22 ° C.), ethoxylated o-phenyl Examples include phenol acrylate, phenoxy polyethylene glycol acrylate, and methoxy polyethylene glycol acrylate. These may be used individually by 1 type and may use 2 or more types together.
Among these, phenoxyethyl acrylate (glass transition temperature Tg: −22 ° C.) and ethoxylated o-phenylphenol acrylate are preferable.

-Multifunctional (meth) acrylate monomer-
There is no restriction | limiting in particular as said polyfunctional (meth) acrylate monomer, Although it can select suitably according to the objective, A cyclic crosslinking agent is more preferable.
This is because by using the polyfunctional (meth) acrylate monomer, the cured product can be heat-resistant without greatly changing the storage elastic modulus at room temperature. When the storage elastic modulus at room temperature changes greatly, the functional film becomes brittle and it becomes difficult to produce the functional film by a roll-to-roll process or the like.
The cyclic crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, dioxane glycol diacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, ethylene oxide modified isocyanuric Examples thereof include acid diacrylate, ethylene oxide-modified isocyanuric acid triacrylate (ethoxylated isocyanuric acid triacrylate), caprolactone-modified tris (acryloxyethyl) isocyanurate, and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, ethylene oxide-modified isocyanuric acid triacrylate (ethoxylated isocyanuric acid triacrylate) is preferable in terms of flexibility.

--2 Functional urethane (meth) acrylate-
The bifunctional urethane (meth) acrylate as an example of the polyfunctional (meth) acrylate monomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, EBECRYL8804, EBECRYL8807, EBECRYL8402 and KRM8296 Manufactured by Daicel Ornex Co., Ltd.), CN9001, CN978, CN962 (manufactured by Sartomer), purple light UV6640B, purple light UV3300B, UV3200B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), TEAI-2000, TE-2000 (or more, Nippon Soda Co., Ltd.). These may be used individually by 1 type and may use 2 or more types together.
Among these, an aliphatic bifunctional acrylate (for example, EBECRYL 8807) is preferable in terms of flexibility and weather resistance.

  There is no restriction | limiting in particular as glass transition temperature of the said bifunctional urethane (meth) acrylate, Although it can select suitably according to the objective, -30 degreeC or more and 45 degrees C or less are preferable. When the glass transition temperature is −30 ° C. or higher and 45 ° C. or lower, the tensile elongation at break and flexibility can be improved. In addition, the glass transition temperature said here points out the value of the homopolymer of the said (meth) acrylate.

  There is no restriction | limiting in particular as content of the said polyfunctional (meth) acrylate monomer in the said photocurable resin composition, Although it can select suitably according to the objective, 30 to 75 mass% is preferable, 50 mass% or more and 75 mass% or less are preferable. Since the polyfunctional (meth) acrylate monomer has high reactivity, when the content is within a preferable range, it is easy to reduce the amount of the photo radical generator remaining in the resin layer.

-Phosphate group-containing acrylate-
By including the phosphoric acid group-containing acrylate as an additive, the adhesion to the inorganic layer can be improved.
The phosphate group-containing acrylate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, di-2-methacrylate. Roxyethyl phosphate, and the like. These may be used individually by 1 type and may use 2 or more types together.

<<< Photoradical generator >>>
The photo radical generator is not particularly limited as long as it is an organic substance that generates radicals by light, and can be appropriately selected according to the purpose.
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184)
2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651) 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173)
2-Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (Irgacure 127)
2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907)
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819)
A mixture of oxyphenylacetic acid 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl ester (Irgacure 745)
, Etc. These may be used individually by 1 type and may use 2 or more types together.
These are sometimes referred to as photopolymerization initiators, radical photopolymerization initiators, and the like.

  There is no restriction | limiting in particular as content of the said photoradical generator in the said photocurable resin composition, Although it can select suitably according to the objective, More than 0.01 mass% and 5.0 mass% or less are preferable. More preferably, more than 0.1 mass% and 3.0 mass% or less.

<<< Other ingredients >>>
As said other component, a silane coupling agent etc. are mentioned, for example.

-Silane coupling agent-
The silane coupling agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxy Examples include silane, 3-methacryloxypropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. These may be used individually by 1 type and may use 2 or more types together.

<< Storage modulus >>
The storage elastic modulus of the resin layer at 25 ° C. is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 × 10 ⁹ Pa or less, more preferably 8.0 × 10 ⁸ Pa or less. preferable. When the storage elastic modulus is in a preferable range, the resin layer is easily stretched, and as a result, the functional film is easily stretched.

The storage elastic modulus can be confirmed as follows, for example. When the surface of the resin layer is exposed, it can be confirmed by measuring the storage elastic modulus of the exposed surface using a micro hardness meter. Moreover, when the 1st base material etc. are formed in the surface of the resin layer, after peeling the 1st base material etc. and exposing the surface of the resin layer, the storage elastic modulus of the exposed surface Can be confirmed by measuring with a microhardness meter.
Further, a test piece corresponding to the resin layer may be prepared, and the storage elastic modulus of the test piece may be measured.

<Adhesive layer>
There is no restriction | limiting in particular as a material of the said adhesion layer, According to the objective, it can select suitably, For example, although an acrylic type, rubber type, polyester type, a silicon type etc. are mentioned, the said adhesion layer is optical characteristics. From the viewpoint of weather resistance, an acrylic adhesive layer is preferred.
The acrylic adhesive layer is an adhesive layer containing an acrylic polymer.
In order to improve weather resistance, the adhesive layer may contain a UV absorber.

  There is no restriction | limiting in particular as average thickness of the said adhesion layer, Although it can select suitably according to the objective, 5 micrometers or more and 30 micrometers or less are preferable, and 10 micrometers or more and 20 micrometers or less are more preferable.

<Other members>
As said other member, an inorganic layer, a base material, etc. are mentioned, for example.

<< Inorganic layer >>
The inorganic layer is disposed on a surface of the resin layer opposite to the adhesive layer side.
The inorganic layer is preferably a reflective layer that reflects at least near infrared rays. Examples of the reflective layer include the following laminated films.
The inorganic layer may have irregularities.

The surface of the inorganic layer on the resin layer side is preferably made of an oxide.
As the oxide is not particularly limited and may be appropriately selected depending on the purpose, for example, oxides composed mainly of ZnO, the oxide mainly composed of Nb ₂ O _5, and the like.

  There is no restriction | limiting in particular as an average film thickness of the said inorganic layer, Although it can select suitably according to the objective, 20 micrometers or less are preferable, 5 micrometers or less are more preferable, and 1 micrometer or less are more preferable.

  There is no restriction | limiting in particular as a formation method of the said inorganic layer, According to the objective, it can select suitably, For example, a sputtering method, a vapor deposition method, the dip coating method, the die coating method etc. can be used.

  There is no restriction | limiting in particular as a kind of said inorganic layer, According to the objective, it can select suitably, For example, a laminated film, a transparent conductive layer, a functional layer, a semi-transmissive layer etc. are mentioned. These may be used alone or in combination of two or more.

<<< Laminated film >>>
The laminated film is not particularly limited and may be appropriately selected depending on the purpose. For example, (i) a laminated film obtained by alternately laminating low refractive index layers and high refractive index layers having different refractive indexes, (Ii) a laminated film formed by alternately laminating a metal layer having a high reflectance in the infrared region, an optical transparent layer having a high refractive index in the visible region and functioning as an antireflection layer, or a transparent conductive layer. It is done.

-Metal layer-
For the metal layer, a metal having a high reflectance in the infrared region is used.
The metal having high reflectivity in the infrared region is not particularly limited and can be appropriately selected according to the purpose. For example, Au, Ag, Cu, Al, Ni, Cr, Ti, Pd, Co, Si, Examples thereof include simple substances such as Ta, W, Mo, and Ge, and alloys containing two or more of these simple substances. Among these, Ag-based, Cu-based, Al-based, Si-based, and Ge-based materials are preferable in terms of practicality.
The alloy is not particularly limited and can be appropriately selected depending on the purpose. Etc. are preferable.
In order to suppress corrosion of the metal layer, it is preferable to add materials such as Ti and Nd to the metal layer. In particular, when Ag is used as the material of the metal layer, it is preferable to add the above material.

-Optical transparent layer-
The optical transparent layer is an optical transparent layer that has a high refractive index in the visible region and functions as an antireflection layer.
There is no restriction | limiting in particular as a material of the said optical transparent layer, According to the objective, it can select suitably, For example, high dielectric materials, such as niobium oxide, a tantalum oxide, a titanium oxide, etc. are mentioned.

  For the purpose of preventing oxidative degradation of the lower layer metal during the formation of the optical transparent layer, a thin buffer layer of Ti or the like of about several nm may be provided at the interface of the optical transparent layer to be formed. Here, the buffer layer is a layer for suppressing oxidation of a metal layer or the like as a lower layer by oxidizing itself when forming the upper layer.

<<< Transparent conductive layer >>>
The transparent conductive layer is a transparent conductive layer mainly composed of a conductive material having transparency in the visible region.
There is no restriction | limiting in particular as said transparent conductive layer, According to the objective, it can select suitably, For example, a tin oxide, zinc oxide, indium tin oxide (ITO), indium zinc oxide (IZO), aluminum dope zinc oxide ( AZO), antimony-doped tin oxide, transparent conductive materials such as carbon nanotube-containing bodies, and the like.
In addition, as the transparent conductive layer, a layer in which nanoparticles of a conductive material such as nanoparticles of the transparent conductive material or metal, nanorods, and nanowires are dispersed in a resin at a high concentration may be used.

<<< Functional layer >>>
The functional layer is a layer mainly composed of a chromic material whose reflection performance is reversibly changed by an external stimulus.
The chromic material is a material that reversibly changes its structure by an external stimulus such as heat, light, or an intruding molecule.
There is no restriction | limiting in particular as said chromic material, According to the objective, it can select suitably, For example, a photochromic material, a thermochromic material, a gas chromic material, an electrochromic material, etc. are mentioned.

The photochromic material is a material that reversibly changes its structure by the action of light.
The photochromic material is a material that can reversibly change physical properties such as reflectance and color by irradiation with light such as ultraviolet rays.
As the photochromic material is not particularly limited and may be appropriately selected depending on the purpose, for example, Cr, Fe, _TiO 2 doped with like _{Ni, WO 3, MoO 3,} Nb 2 O 5 transition metal such as And oxides. Moreover, wavelength selectivity can also be improved by laminating | stacking the layer from which these layers and refractive indexes differ.

The thermochromic material is a material that reversibly changes its structure by the action of heat.
The thermochromic material can reversibly change various physical properties such as reflectance and color by heating.
As the thermochromic material is not particularly limited and may be appropriately selected depending on the purpose, for example, VO _2, and the like. Further, for the purpose of controlling the transition temperature and the transition curve, elements such as W, Mo, and F can be added.
Alternatively, a laminated structure in which a thin film mainly composed of a thermochromic material such as VO ₂ is sandwiched between antireflection layers mainly composed of a high refractive index body such as TiO ₂ or ITO may be employed.

  Alternatively, a photonic lattice such as cholesteric liquid crystal can be used. The cholesteric liquid crystal can selectively reflect light having a wavelength corresponding to the layer interval, and the layer interval changes depending on the temperature. Therefore, the physical properties such as reflectance and color can be reversibly changed by heating. it can. At this time, it is possible to widen the reflection band by using several cholesteric liquid crystal layers having different layer intervals.

An electrochromic material is a material that can reversibly change various physical properties such as reflectance and color by electricity.
As the electrochromic material, for example, a material that reversibly changes its structure by applying a voltage can be used. A specific example of the electrochromic material is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a reflective light-modulating material whose reflection characteristics are changed by doping or dedoping such as proton. It is done.
Specifically, the reflection-type light control material is a material that can control its optical properties to a transparent state, a mirror state, and / or an intermediate state by an external stimulus. As the reflection type light modulating material is not particularly limited and may be appropriately selected depending on the purpose, for example, alloy materials, WO ₃ to alloy magnesium and nickel, an alloy material of magnesium and titanium as main components And a material in which needle-shaped crystals having selective reflectivity are confined in a microcapsule.

The specific configuration of the functional layer is not particularly limited and may be appropriately selected depending on the purpose. For example, (i) a catalyst layer containing the alloy layer, Pd, etc. on the resin layer, thin Al, etc. A buffer layer, an electrolyte layer such as Ta ₂ O ₅ , an ion storage layer such as WO ₃ containing protons, and a transparent conductive layer, (ii) a transparent conductive layer, an electrolyte layer, WO _{3 and the} like on the resin layer The electrochromic layer of this, the structure by which the transparent conductive layer was laminated | stacked, etc. are mentioned.
In these configurations, by applying a voltage between the transparent conductive layer and the counter electrode, protons contained in the electrolyte layer are doped or dedoped in the alloy layer. Thereby, the transmittance | permeability of an alloy layer changes. In order to improve wavelength selectivity, it is desirable to laminate an electrochromic material with a high refractive index material such as TiO ₂ or ITO.
Other configurations include a transparent conductive layer, an optical transparent layer in which microcapsules are dispersed, and a transparent electrode laminated on a resin layer. In this configuration, by applying a voltage between both transparent electrodes, the acicular crystal in the microcapsule is in a transmission state in which it is oriented, or by removing the voltage, the acicular crystal is directed in all directions to be in a wavelength selective reflection state. can do.

<<< Semi-transmissive layer >>>
The semi-transmissive layer is made of, for example, a single layer or a plurality of metal layers and has semi-transmissibility.
There is no restriction | limiting in particular as a material of the said metal layer, According to the objective, it can select suitably, For example, the thing similar to the metal layer of the above-mentioned laminated film can be used.

<< Base material >>
The substrate usually has transparency.
It is preferable that the base material has energy ray permeability.
There is no restriction | limiting in particular as a material of the said base material, According to the objective, it can select suitably, For example, a triacetyl cellulose (TAC), polyester (TPEE), a polyethylene terephthalate (PET), a polyimide (PI), polyamide (PA), aramid, polyethylene (PE), polyacrylate, polyether sulfone, polysulfone, polypropylene (PP), diacetyl cellulose, polyvinyl chloride, acrylic resin (PMMA), polycarbonate (PC), epoxy resin, urea resin, Examples thereof include urethane resin and melamine resin.
There is no restriction | limiting in particular as average thickness of the said base material, Although it can select suitably according to the objective, 38 micrometers or more and 100 micrometers or less are preferable from a viewpoint of productivity.

Hereinafter, another embodiment of the functional film will be described in detail.
Another embodiment of the functional film includes a first optical layer having an uneven surface, the inorganic layer disposed on the uneven surface of the first optical layer, and another uneven surface on the inorganic layer side. A second optical layer having a surface and disposed so that the unevenness on the other uneven surface is buried, and the second optical layer is the resin layer. Such a functional film is a film (heat ray retroreflective film having wavelength selective reflectivity) that transmits visible light of incident light and that can be retroreflected by selecting infrared rays.

FIG. 5 is a cross-sectional view of an example of a functional film according to another embodiment of the present invention.
In FIG. 5, the functional film 11 includes a first optical layer 2 having an uneven surface 2a, an inorganic layer 1 disposed on the uneven surface 2a of the first optical layer 2, and other layers on the inorganic layer 1 side. On the surface 2b opposite to the uneven surface 2a of the first optical layer 2 and the resin layer 3 (second optical layer) which has the uneven surface 3a and is arranged so that the unevenness on the other uneven surface 3a is buried. And a first base material 4 disposed on the surface. The functional film 11 does not have the second base material disposed on the surface 3b (external support side) facing the other uneven surface 3a of the resin layer 3 (second optical layer). As shown, the resin layer 3 (second optical layer) is used in contact with the adhesive layer 5.

<First optical layer>
The first optical layer has an uneven surface.
The first optical layer supports and protects the inorganic layer formed on the uneven surface.
The first optical layer is composed of a resin-based layer, for example, from the viewpoint of imparting flexibility to the functional film. Of the two main surfaces of the first optical layer, for example, one surface is a smooth surface and the other surface is an uneven surface (first surface). The inorganic layer is disposed on the uneven surface (first surface).

  There is no restriction | limiting in particular as the minimum value of the thickness of a said 1st optical layer, According to the objective, it can select suitably.

The first optical layer is, for example, a cured product of a photocurable resin composition.
The composition of the photocurable resin composition for forming the first optical layer may be the same as or different from the composition of the photocurable resin composition for forming the resin layer. However, different compositions are usually selected in consideration of optical characteristics and the like.

<< Storage modulus >>
The storage elastic modulus at 25 ° C. of the first optical layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 × 10 ⁹ Pa or less, and 8.0 × 10 ⁸ Pa. The following is more preferable. When the storage elastic modulus is in a preferable range, the first optical layer is easily stretched, and as a result, the functional film is easily stretched.

  The first optical layer preferably has a higher storage elastic modulus and is harder than the second optical layer. This is achieved by including a polyfunctional (meth) acrylate monomer in the resin constituting the first optical layer.

<Inorganic layer>
The inorganic layer is a layer disposed on the uneven surface of the first optical layer, and is the aforementioned inorganic layer.
The inorganic layer is preferably a reflective layer that reflects at least near infrared rays. Examples of the reflective layer include the aforementioned laminated film. Details of an example of the reflective layer will be described later with reference to FIG.

<Second optical layer>
The second optical layer, which is the resin layer, has another uneven surface (second surface) on the inorganic layer side so that the unevenness on the other uneven surface (second surface) is buried. Arranged (formed) to protect the inorganic layer.
The second optical layer is, for example, a cured product of the photocurable resin composition.

  Of the two main surfaces of the second optical layer, for example, one surface is a smooth surface and the other surface is another uneven surface (second surface). The uneven surface of the first optical layer and the other uneven surface of the second optical layer are in a relationship in which the unevenness is reversed.

<< Minimum value of thickness of second optical layer >>
The minimum value of the thickness of the second optical layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 μm or more, more preferably 2 μm or more and 40 μm or less, and further 2 μm or more and 25 μm or less. More preferably, it is 2 μm or more and 10 μm or less. When the minimum value of the thickness of the second optical layer is 2 μm or more, the prism effect can be reduced and sufficient transparency can be obtained.
The minimum value of the thickness of the second optical layer is represented by, for example, “A” in FIG. 7, and “the thickness of the second optical layer when the thickness of the first optical layer is maximum”. means.

<< Storage modulus >>
The storage elastic modulus at 25 ° C. of the second optical layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 × 10 ⁹ Pa or less, and 8.0 × 10 ⁸ Pa. The following is more preferable. When the storage elastic modulus is in a preferable range, the second optical layer is easily stretched, and as a result, the functional film is easily stretched.

It is preferable that at least one of the first optical layer and the second optical layer contains a resin having a storage elastic modulus at 25 ° C. of 3 × 10 ⁹ Pa or less. This is because flexibility can be imparted to the functional film at room temperature of 25 ° C., so that the functional film can be produced in a roll-to-roll manner.

<Tensile breaking elongation>
The tensile elongation at break of the functional film is 60% or more, preferably 60% or more and 1,000% or less, and more preferably 60% or more and 500% or less.
When the tensile elongation at break of the functional film is 60% or more, it can be adapted to the “glass scattering prevention film” defined in JIS-A5759.

The tensile elongation at break of the functional film is measured, for example, by the following method.
Measurement is performed according to JIS A5759 2008. A test piece having a test length of 100 mm and a width of 25 mm is prepared, a tensile test is performed three times at a test speed of 300 mm / min, and an average value of strain at the time of breaking is measured.

<Wavelength selective reflectivity>
FIG. 8 is a perspective view showing a relationship between incident light incident on the functional film 11 having wavelength selective reflectivity and reflected light reflected by the functional film 11. The functional film 11 has an incident surface S1 on which the light L is incident. Functional film 11, the angle of incidence (theta, phi) among the light L incident on the incident surface S1, selectively specular (-θ, φ + 180 °) than the directivity in the direction of the light L ₁ in a specific wavelength band whereas it reflects and transmits light L ₂ other than the specific wavelength band. Moreover, the functional film 11 has transparency with respect to light other than the specific wavelength band. As transparency, it is preferable that it has the range of the transmitted image clarity mentioned later. However, theta: the perpendicular l ₁ with respect to the incident surface S1, is an angle formed between the incident light L or the reflected light L _1. phi: a specific linearly l ₂ within the incident surface S1, is an angle formed between the projection and the component on the incident surface S1 and the incident light L or the reflected light L _1. Here, the specific straight line l ₂ in the incident surface means that the incident angle (θ, φ) is fixed and the functional film 11 is rotated about the perpendicular l ₁ with respect to the incident surface S ₁ of the functional film 11. , The axis that maximizes the reflection intensity in the φ direction. However, when there are a plurality of axes (directions) at which the reflection intensity is maximum, one of them is selected as the straight line l ₂ . The angle θ rotated clockwise with respect to the perpendicular line ₁₁ is defined as “+ θ”, and the angle θ rotated counterclockwise is defined as “−θ”. The angle φ rotated clockwise with respect to the straight line ₁₂ is defined as “+ φ”, and the angle φ rotated counterclockwise is defined as “−φ”.

  The light of a specific wavelength band that selectively and directionally reflects and the specific light that is transmitted differ depending on the application of the functional film 11. For example, when the functional film 11 is applied to a window material as an external support, the light of a specific wavelength band that selectively reflects light is near infrared light, and the light of a specific wavelength band to be transmitted is Visible light is preferred. Specifically, it is preferable that light in a specific wavelength band that is selectively directionally reflected is mainly near-infrared light having a wavelength band of 780 nm to 2100 nm. By reflecting near infrared rays, when a functional film is bonded to a window material such as a glass window, an increase in temperature in the building can be suppressed. Therefore, the cooling load can be reduced and energy saving can be achieved. Here, the directional reflection means that the reflected light intensity in a specific direction other than the regular reflection is stronger than the regular reflected light intensity and sufficiently stronger than the diffuse reflection intensity having no directivity. Here, “reflecting” means that the reflectance in a specific wavelength band, for example, near infrared region is preferably 30% or more, more preferably 50% or more, and further preferably 80% or more. Transmitting means that the transmittance in a specific wavelength band, for example, in the visible light region is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more.

  In the functional film 11 having wavelength selective reflectivity, it is preferable that the direction φo of direct reflection is −90 ° or more and 90 ° or less. This is because when the functional film 11 is attached to the external support, light in a specific wavelength band can be returned to the sky direction among the light incident from the sky. When there are no tall buildings around, the functional film 11 in this range is useful. Further, the direction of directional reflection is preferably in the vicinity of (θ, −φ). The vicinity means a deviation within a range of preferably within 5 degrees from (θ, −φ), more preferably within 3 degrees, and even more preferably within 2 degrees. By making this range, when the functional film 11 is attached to the external support, among the light incident from above the buildings with the same height, the light of a specific wavelength band is efficiently over the other buildings. It is because it can return well. In order to realize such directional reflection, it is preferable to use a three-dimensional structure such as a spherical surface, a part of a hyperboloid, a triangular pyramid, a quadrangular pyramid, or a cone. The light incident from the (θ, φ) direction (−90 ° <φ <90 °) is based on the shape (θo, φo) direction (0 ° <θo <90 °, −90 ° <φo <90 ° ) Can be reflected. Alternatively, a columnar body extending in one direction is preferable. Light incident from the (θ, φ) direction (−90 ° <φ <90 °) is reflected in the (θo, −φ) direction (0 ° <θo <90 °) based on the inclination angle of the columnar body. Can do.

  In the functional film 11 having wavelength selective reflectivity, the directional reflection of the light in the specific wavelength band is in the direction near the retroreflection, that is, in the specific wavelength band with respect to the light incident on the incident surface S1 at the incident angle (θ, φ). The light reflection direction is preferably in the vicinity of (θ, φ). This is because, when the functional film 11 is pasted on the external support, light in a specific wavelength band can be returned to the sky among the light incident from the sky. Here, the vicinity is preferably within 5 degrees, more preferably within 3 degrees, and further preferably within 2 degrees. This is because, when the functional film 11 is attached to the external support, the light in the specific wavelength band can be efficiently returned to the sky among the light incident from the sky. In addition, when the infrared light irradiation part and the light receiving part are adjacent to each other, such as an infrared sensor or infrared imaging, the retroreflection direction must be the same as the incident direction, but there is no need to sense from a specific direction Need not be in exactly the same direction.

<Uneven shape>
As shown in FIG. 9A, the shape of the structure 2c constituting the first optical layer 2 may have a asymmetrical shape with respect to the vertical perpendicular line l ₁ to the incident surface S1 or the emission surface S2 of the functional film 11 . In this case, the main axis l _m of the structure 2c is inclined in the arrangement direction a of the structures 2c with respect to the perpendicular l ₁ . Here, the main axis l _m of the structure 2c means a straight line passing through the midpoint of the bottom of the structure cross section and the apex of the structure. When the functional film 11 is pasted on a window material as an external support disposed substantially perpendicular to the ground, the main axis l _m of the structure 2c is based on the perpendicular l ₁ as shown in FIG. 9B. It is preferable to incline downward (on the ground side) of the window material as an external support. In general, the heat inflow through the window is mostly in the time zone around noon, and the altitude of the sun is often higher than 45 °. Therefore, by adopting the above shape, the light incident from these high angles can be efficiently used. This is because it can be reflected upward. In Figure 9A and 9B, examples of the asymmetric shape is shown with respect to the perpendicular line l ₁ of the structure 2c of the prism shape. It is also a asymmetrical shape with respect to the perpendicular line l ₁ of the structure 2c other than prism-shaped. For example, the corner cube body may have an asymmetric shape with respect to the perpendicular l ₁ .

  When the structure 2c has a prism shape, the inclination angle α (FIG. 5) of the prism-shaped structure 2c is, for example, 45 °. When applied to a window member, the structure 2c preferably has a flat surface or curved surface with an inclination angle of 45 ° or more as much as possible from the viewpoint of reflecting a large amount of light incident from above and returning it to the sky. By adopting such a shape, incident light returns to the sky with almost one reflection, so even if the reflectivity of the wavelength selective reflection film is not so high, the incident light can be reflected efficiently in the upward direction and the wavelength can be selected. This is because light absorption in the reflective film can be reduced.

  FIG. 10A is a plan view illustrating a configuration example of the first optical layer in the functional film according to the embodiment of the present invention. 10B is a cross-sectional view of the first optical layer shown in FIG. 10A taken along line BB.

  On one main surface of the first optical layer 2, the structures 2c are two-dimensionally arranged. This arrangement is preferably the arrangement in the closest packed state. For example, on one main surface of the first optical layer 2, a dense array such as a delta dense array is formed by two-dimensionally arranging the structures 2c in a most densely packed state. As shown in FIGS. 10A to 10B, for example, the delta dense array is a structure in which structures 2c (for example, triangular pyramids) having a triangular bottom surface are arranged in a close-packed state.

  Further, the shape of the structure 2c formed on the surface of the first optical layer 2 is not limited to one type, and a plurality of types of structures 2c are formed on the surface of the first optical layer. It may be. When a plurality of types of structures 2c are provided on the surface, a predetermined pattern composed of a plurality of types of structures 2c may be periodically repeated. Further, depending on desired characteristics, a plurality of types of structures 2c may be formed randomly (non-periodically).

<Method for producing functional film>
Hereinafter, with reference to FIGS. 11A to 11C, FIGS. 12A to 12C, and FIGS. 13A to 13D, an example of a method for producing a functional film according to an embodiment of the present invention will be described. Note that part or all of the manufacturing process described below is preferably performed by roll-to-roll in consideration of productivity. However, the mold manufacturing process is excluded.

  First, as shown in FIG. 11A, the die 21 has the same concave-convex shape as that of the structure 2c constituting the first optical layer 2 or the inverted shape of the die 21 by, for example, bite processing or laser processing. A mold (replica) is formed. Next, as shown in FIG. 11B, the uneven shape of the mold 21 is transferred to a film-like resin material by using, for example, a melt extrusion method or a transfer method. As a transfer method, a photo-curable resin composition is poured into a mold and cured by irradiating energy rays, a method of transferring heat and pressure to the resin to transfer the shape, or a resin film is supplied from a roll and heated. For example, a method of transferring the shape of the mold while adding (laminate transfer method) can be used. Thereby, as shown in FIG. 11C, the first optical layer 2 having the structure 2c on one principal surface is formed.

  Further, as shown in FIG. 11C, the first optical layer 2 may be formed on the first substrate 4. In this case, for example, the film-like first substrate 4 is supplied from a roll, and after the photocurable resin composition is applied onto the first substrate 4, it is pressed against the mold to change the shape of the mold. A method is used in which the photocurable resin composition is cured by transferring and irradiating energy rays such as ultraviolet rays.

  Next, as shown in FIG. 12A, a wavelength selective reflection layer (functional layer) as the inorganic layer 1 is formed on one main surface of the first optical layer 2. The film forming method of the wavelength selective reflection layer as the inorganic layer 1 is not particularly limited and can be appropriately selected according to the purpose. For example, sputtering method, vapor deposition method, CVD (Chemical Vapor Deposition) method, dip coating Method, die coating method, wet coating method, spray coating method and the like, and it is preferable to select from these film forming methods according to the shape of the structure 2c and the like. Next, as shown in FIG. 12B, annealing treatment 31 is applied to the wavelength selective reflection layer as the inorganic layer 1 as necessary. The annealing temperature is, for example, in the range of 100 ° C. or higher and 250 ° C. or lower.

Next, as shown in FIG. 12C, the photocurable resin composition 22 is applied on the wavelength selective reflection layer as the inorganic layer 1.
Next, as shown in FIG. 13A, the laminate is formed by spreading the photocurable resin composition 22 to a predetermined thickness using a coater or the like to fill the uneven structure.
Next, as shown in FIG. 13B, for example, the photocurable resin composition 22 is cured by the energy rays 32 and a pressure 33 is applied to the laminate. There is no restriction | limiting in particular as said energy beam, According to the objective, it can select suitably, For example, an electron beam, an ultraviolet-ray, visible light, a gamma ray, an electron beam etc. are mentioned. Among these, ultraviolet rays are preferable from the viewpoint of production equipment. There is no restriction | limiting in particular as integrated irradiation amount, It can select suitably considering the hardening characteristic of resin, the yellowing suppression of resin or a base material, etc. There is no restriction | limiting in particular as a pressure added to a laminated body, Although it can select suitably according to the objective, 0.01 MPa or more and 1 MPa or less are preferable. If the pressure applied to the laminate is less than 0.01 MPa, there is a problem in the running property of the film. On the other hand, if it exceeds 1 MPa, it is necessary to use a metal roll as the nip roll, and pressure unevenness is likely to occur.
As described above, as shown in FIG. 13C, the resin layer 3 (second optical layer) is formed on the wavelength selective reflection layer as the inorganic layer 1, and the functional film 11 is obtained.
Further, in the functional film of the present invention, the adhesive layer 5 may be formed on the side opposite to the inorganic layer 1 side of the resin layer 3 (second optical layer). There is no restriction | limiting in particular as a formation method of the adhesion layer 5, According to the objective, it can select suitably, For example, it forms by apply | coating an adhesive composition on the resin layer 3 (2nd optical layer). Alternatively, it may be formed by laminating the resin layer 3 (second optical layer) and the adhesive layer 5 by lamination.
The flatness of the surface 3b facing the other uneven surface 3a of the resin layer 3 (second optical layer) is caused by the flatness of the coater head or the like and the thickness of the resin (the degree of unevenness filling). .

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example.

(Example 1-1)
<Preparation of anti-scattering / security film>
After applying the following photocurable resin composition B1 on a PET base material A4300 (base material 1: manufactured by Toyobo Co., Ltd., thickness 50 μm), the resin layer (average thickness 20 μm) is formed by irradiating with ultraviolet rays and curing. I got a scattering prevention / crime prevention film.

<< Photocurable resin composition B >>
The materials described in Table 1 below were mixed to obtain photocurable resin compositions B1 to B4.

Details of the materials in Table 1 are as follows.
EBECRYL 8807: bifunctional urethane acrylate, manufactured by Daicel Ornex Co., Ltd. ACMO: acryloylmorpholine as a monofunctional acrylate monomer having a nitrogen-containing heterocyclic ring, manufactured by KJ Chemicals, glass transition temperature Tg: 145 ° C
A-600: polyethylene glycol # 600 diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. NK-ester AMP-10G: phenoxyethyl acrylate as a monofunctional acrylate monomer having an alkylene oxide chain, manufactured by Shin-Nakamura Chemical Co., Ltd., glass Transition temperature Tg: −22 ° C.
-KAYARAD FM-400: 2,2-dimethyl-3- (acryloyloxy) propionic acid 2,2-dimethyl-3- (acryloyloxy) propyl, manufactured by Nippon Kayaku Co., Ltd.-Aronix M-211B: polyfunctional acrylate monomer Bisphenol A EO-modified (n≈2) diacrylate, manufactured by Toagosei Co., Ltd. ・ Irgacure 184: photoradical generator (photopolymerization initiator), manufactured by BASF Japan Ltd.

<Water absorption rate>
The water absorption rate of the resin layer or the layer to be measured was determined by the following method based on JIS K 7209: 2000.
The resin layer or the layer to be measured was isolated, measured for mass (M ₀ ), and immersed in water at 25 ° C. for 24 hours. Thereafter, the water on the surface was sufficiently wiped off, and the mass (M ₂₄ ) was measured. The water absorption rate (mass%) was determined by the following formula.
Water absorption (mass%) = (M ₂₄ −M ₀ ) / M ₀

<Drainage test>
An adhesive layer (average thickness of 16 μm, MF58UV0455, manufactured by Yodogawa Paper Mill) was attached to the resin layer of the obtained film. And it used for the following drainage tests. The results are shown in Table 3-1.
The water sticking method was performed by the following method. An appropriate amount of the coating liquid (water) was applied to glass as an external support, and then the adhesive layer was attached to the external support. At that time, the squeegee was pressed against the film and applied while extruding the coating solution, and the coating solution (water) was discharged from between the adhesive layer and the external support. The coating liquid (water) was not completely discharged, and a small amount remained between the adhesive layer and the external support to form a convex portion. Then, the state of the convex part was confirmed visually after leaving at 23 degreeC for 72 hours and 168 hours.
〔Evaluation criteria〕
○: Convex parts are not confirmed.
Δ: Slightly visible convex portions, but no problem in use.
Δ: The presence of the convex portion can be confirmed, but it is clearly smaller than the initial state, and there is no problem in use.
X: Existence of convex portions can be confirmed, the size thereof is almost the same as the initial state, and there is a problem in use.

(Examples 1-2 to 1-3, Comparative Example 1-1)
In Example 1-1, except for changing the photocurable resin composition B1 to the photocurable resin composition shown in Table 3-1, in the same manner as in Example 1-1, the scattering prevention / security film Was made.
The produced scattering prevention / security film was evaluated in the same manner as in Example 1-1. The results are shown in Table 3-1.

(Comparative Example 1-2)
A PET base material A4300 (base material 1: manufactured by Toyobo Co., Ltd., thickness: 50 μm) alone was used as a scattering prevention / security film.
The produced scattering prevention / security film was evaluated in the same manner as in Example 1-1. The results are shown in Table 3-1.

(Comparative Example 1-3)
On the PET base material A4300 (base material 1: manufactured by Toyobo Co., Ltd., thickness 50 μm), the photocurable resin composition B4 is applied so that the average thickness after curing is 20 μm, and further on the PET base material. A4300 (Substrate 2: manufactured by Toyobo Co., Ltd., thickness: 50 μm) was stacked and cured by irradiation with ultraviolet rays to obtain a scattering prevention / security film.
The produced scattering prevention / security film was evaluated in the same manner as in Example 1-1. The results are shown in Table 3-1.

(Example 2-1)
<Preparation of thermal barrier film>
On the PET base material A4300 (base material 1: manufactured by Toyobo Co., Ltd., thickness: 50 μm), an inorganic layer having the following constitution was formed by a vacuum sputtering method. Then, after apply | coating the said photocurable resin composition B1 on the said inorganic layer, ultraviolet rays were irradiated and hardened, the resin layer (average thickness of 20 micrometers) was formed, and the heat shield film was obtained.
About the produced heat insulation film, evaluation similar to Example 1-1 was performed. The results are shown in Table 3-2.

<< Structure of inorganic layer >>
(Substrate 1) / Nb ₂ O ₅ (32 nm) / AgPdCu (11 nm) / Al ₂ O ₃ —ZnO (8 nm) / Nb ₂ O ₅ (70 nm) / AgPdCu (11 nm) / AZO (32 nm)

(Examples 2-2 to 2-3, Comparative Example 2-1)
In Example 2-1, a heat-shielding film was produced in the same manner as in Example 2-1, except that the photocurable resin composition B1 was changed to the photocurable resin composition described in Table 3-2. did.
About the produced heat insulation film, evaluation similar to Example 2-1 was performed. The results are shown in Table 3-2.

(Comparative Example 2-2)
On the PET base material A4300 (base material 1: manufactured by Toyobo Co., Ltd., thickness: 50 μm), the inorganic layer having the above-described structure was formed by vacuum sputtering. Thus, a heat shield film was obtained.
About the produced heat insulation film, evaluation similar to Example 2-1 was performed. The results are shown in Table 3-2.
In the water drainage test, an adhesive layer (average thickness 16 μm, MF58UV0455, manufactured by Yodogawa Paper Mill) was attached to the inorganic layer of the obtained heat shielding film.

(Comparative Example 2-3)
On the PET base material A4300 (base material 1: manufactured by Toyobo Co., Ltd., thickness: 50 μm), the inorganic layer having the above-described structure was formed by vacuum sputtering. Subsequently, on the inorganic layer, the photo-curable resin composition B4 was applied so that the average thickness after curing was 20 μm, and further, PET base material A4300 (base material 2: manufactured by Toyobo Co., Ltd., A heat shielding film was obtained by irradiating and curing ultraviolet rays.
About the produced heat insulation film, evaluation similar to Example 2-1 was performed. The results are shown in Table 3-2.
In the water drainage test, an adhesive layer (average thickness: 16 μm, MF58UV0455, manufactured by Yodogawa Paper Mill) was attached to the base 2 of the obtained heat shielding film.

(Example 3-1)
<Preparation of heat ray recursive film>
Using a transfer mold having a two-dimensional parallel groove, the following photocurable resin composition A1 is used on a PET base material A4300 (base material 1: manufactured by Toyobo Co., Ltd., thickness 50 μm). 1 optical layer (resin layer) was formed. On the formed 1st optical layer, the inorganic layer of the following structure was formed by the vacuum sputtering method. On the formed inorganic layer, the said photocurable resin composition B1 was apply | coated, and it irradiated and hardened | cured with the ultraviolet-ray, and formed the 2nd optical layer (resin layer). The heat ray recursive film was obtained by the above. The thickness of the thinnest part of the second optical layer after curing was 20 μm. The thickness of the heat ray recursive film was 85 μm.
About the produced heat ray | wire recursive film, evaluation similar to Example 1-1 was performed. The results are shown in Table 3-3.

<< Structure of inorganic layer >>
(First optical layer) / Nb ₂ O ₅ (32 nm) / AgPdCu (11 nm) / Al ₂ O ₃ —ZnO (8 nm) / Nb ₂ O ₅ (70 nm) / AgPdCu (11 nm) / AZO (32 nm)

<< Photocurable resin composition A >>
The materials described in Table 2 below were mixed to obtain a photocurable resin composition A1.

Details of the materials in Table 2 are as follows.
EBECRYL 8807: bifunctional urethane acrylate, manufactured by Daicel Ornex Co., Ltd. ACMO: acryloylmorpholine as a monofunctional acrylate monomer having a nitrogen-containing heterocyclic ring, manufactured by KJ Chemicals, glass transition temperature Tg: 145 ° C
A-NOD-N: 1,9-nonanediol diacrylate as a polyfunctional acrylate monomer, manufactured by Shin-Nakamura Chemical Co., Ltd., glass transition temperature Tg: 67 ° C.
NK ester A9300: ethoxylated isocyanuric acid triacrylate as a polyfunctional acrylate monomer, manufactured by Shin-Nakamura Chemical Co., Ltd. Irgacure 127: photoradical generator (photopolymerization initiator), manufactured by BASF Japan

(Examples 3-2 to 3-3, Comparative Example 3-1)
In Example 3-1, a heat ray recursive film was produced in the same manner as in Example 3-1, except that the photocurable resin composition B1 was changed to the photocurable resin composition described in Table 3-3. did.
About the produced heat ray | wire recursive film, evaluation similar to Example 3-1 was performed. The results are shown in Table 3-3.

(Comparative Example 3-2)
Using a transfer mold having a two-dimensional parallel groove, the photocurable resin composition A1 is used on a PET base material A4300 (base material 1: manufactured by Toyobo Co., Ltd., thickness 50 μm). 1 optical layer (resin layer) was formed. On the formed first optical layer, the inorganic layer having the above structure was formed by vacuum sputtering. The photocurable resin composition B4 was applied on the formed inorganic layer. Further thereon, a PET base material A4300 (base material 2: manufactured by Toyobo Co., Ltd., thickness 50 μm) was placed and cured by irradiation with ultraviolet rays to obtain a heat ray recursive film. The thickness of the thinnest part of the second optical layer after curing was 20 μm. The thickness of the heat ray recursive film was 85 μm.
About the produced heat ray | wire recursive film, evaluation similar to Example 3-1 was performed. The results are shown in Table 3-3.

  From the above, it has been found that the convexity caused by water when water is applied can be made inconspicuous over time by setting the water absorption rate of the resin layer of the functional film to 2.0 mass% or more.

  The functional film of the present invention can be applied in a wide variety of applications, and in particular, can be suitably used as a functional film to be attached to a window glass, a wall or the like.

DESCRIPTION OF SYMBOLS 1 Inorganic layer 2 1st optical layer 2a Irregular surface 2b Surface 3a Irregular surface 3 Resin layer 4 1st base material 5 Adhesive layer 11 Functional film 22 Photocurable resin composition

Claims (9)

A functional film having a resin layer used in contact with the adhesive layer,
A functional film, wherein the resin layer has a water absorption of 2.0% by mass or more.   The functional film according to claim 1, wherein the water absorption of the resin layer is 5.0% by mass or more.   The functional film according to claim 1, wherein the water absorption of the resin layer is 10% by mass or more.   The functional film in any one of Claim 1 to 3 which has an inorganic layer on the surface on the opposite side to the said adhesion layer side in the said resin layer.   The functional film according to claim 4, wherein the inorganic layer has irregularities. A first optical layer having an uneven surface;
The inorganic layer disposed on the uneven surface of the first optical layer;
A second optical layer having another uneven surface on the inorganic layer side and disposed so that the unevenness on the other uneven surface is buried;
Have
The functional film according to claim 4, wherein the second optical layer is the resin layer.   The functional film according to claim 1, wherein the resin layer is a cured product of a photocurable resin composition.   The functional film according to claim 7, wherein the photocurable resin composition contains a polyfunctional (meth) acrylate monomer and a monofunctional (meth) acrylate compound. The functional film according to claim 8, wherein the monofunctional (meth) acrylate compound contains acryloylmorpholine.