WO2019216384A1 - Multilayer body and method for producing same, and fresnel mirror and method for producing same - Google Patents

Abstract

The present invention provides a Fresnel mirror which has an antifouling layer on the viewing-side surface, and which is configured such that the antifouling layer has a water repellent molecular structure.

Description

Laminated body, manufacturing method thereof, Fresnel mirror, and manufacturing method thereof

The present invention relates to a laminate used for a Fresnel mirror, a manufacturing method thereof, a Fresnel mirror, and a manufacturing method thereof.

The Fresnel mirror has a function of a convex mirror or a concave mirror although it is a flat shape as well known in Patent Document 1 and the like. Fresnel mirrors can be made thinner than conventional convex mirrors, so they can be installed on the walls of passages such as T-shaped, L-shaped, and crossroads to check blind spots around the corners of the passage. It doesn't get in the way. Therefore, Fresnel mirrors having a convex mirror function are installed in intersections and the like, and are used as collision prevention means for checking blind spots (for example, see Patent Document 2). The Fresnel mirror can also be used as a mirror for confirming the rear. Therefore, Fresnel mirrors are installed in a wide range of locations, including ATMs (automatic teller machines), convenience stores, roadways, office buildings, factories, railways, and airplanes.

JP-A-6-174906 JP 2012-88565 A

As described above, since the Fresnel mirror is used as a collision prevention means for confirming blind spots, a rear confirmation means, etc., it is required to have good visibility.

An object of the present invention is to provide a Fresnel mirror excellent in antifouling property, a manufacturing method thereof, a laminate used for the Fresnel mirror, and a manufacturing method thereof.

Means for solving the problems are as follows. That is,
<1> Having a laminate including an antifouling layer and a resin layer,
The laminate has heat resistance,
The Fresnel mirror characterized in that the antifouling layer is disposed on the surface on the viewing side and has a water-repellent molecular structure.
Here, the heat resistance means that the laminate is placed on a hot plate set at 250 ° C. with the antifouling layer side up and held for 5 minutes, and then visually observed to prevent cracking or discoloration. means.
<2> Having an antifouling layer on the surface on the viewing side,
The antifouling layer has a water-repellent molecular structure;
The water repellent molecular structure is derived from a water repellent monomer having fluorine,
The antifouling layer is a curable resin composition containing the water-repellent monomer (however, a polyisocyanate which is a diisocyanate trimer, a perfluoropolyether having active hydrogen, a silane compound containing active hydrogen, and Except for the case of containing a carbon-carbon double bond-containing compound obtained by reacting a compound having an active hydrogen containing a monomer having an active hydrogen and a carbon-carbon double bond). It is a Fresnel mirror characterized by
<3> The Fresnel mirror according to any one of <1> to <2>, wherein a water contact angle of a surface on the viewing side of the antifouling layer is 110 ° or more and a hexadecane contact angle is 60 ° or more. is there.
<4> The Fresnel mirror according to any one of <1> to <3>, wherein the surface energy on the viewing side of the antifouling layer is 16 mJ / m ² or less.
<5> The Fresnel mirror according to any one of <1> to <4>, wherein a dynamic friction coefficient of a surface on the viewing side of the antifouling layer is 0.40 or less.
<6> The Fresnel mirror according to any one of <1> to <5>, wherein an elastic recovery rate of the antifouling layer is 50% or more.
<7> The Fresnel mirror according to <1>, wherein the water-repellent molecular structure is derived from a water-repellent monomer having fluorine.
<8> The antifouling layer is a cured product of the curable resin composition,
The Fresnel mirror according to any one of <2> and <7>, wherein the curable resin composition contains the water-repellent monomer.
<9> The Fresnel mirror according to <8>, wherein the curable resin composition contains a bifunctional or higher functional (meth) acrylate.
<10> The Fresnel mirror according to <9>, wherein the bifunctional or higher functional (meth) acrylate has a ring structure.
<11> The antifouling layer,
A resin layer having a multi-step inclined surface like a Fresnel lens on the surface opposite to the viewing side;
A light reflecting layer disposed on a surface of the resin layer having the inclined surface;
The Fresnel mirror according to any one of <1> to <10>.
<12> A heat-resistant laminate used for a Fresnel mirror,
An antifouling layer having a water-repellent molecular structure;
A resin layer;
It is a laminated body characterized by having.
Here, the heat resistance means that the laminate is placed on a hot plate set at 250 ° C. with the antifouling layer side up and held for 5 minutes, and then visually observed to prevent cracking or discoloration. means.
<13> A laminate used for a Fresnel mirror,
An antifouling layer having a water-repellent molecular structure;
A resin layer;
Have
The water repellent molecular structure is derived from a water repellent monomer having fluorine,
The antifouling layer is a curable resin composition containing the water-repellent monomer (however, a polyisocyanate which is a diisocyanate trimer, a perfluoropolyether having active hydrogen, a silane compound containing active hydrogen, and Except for the case of containing a carbon-carbon double bond-containing compound obtained by reacting a compound having an active hydrogen containing a monomer having an active hydrogen and a carbon-carbon double bond). It is the laminated body characterized by these.
<14> The laminate according to any one of <12> to <13>, wherein the surface of the antifouling layer has a water contact angle of 110 ° or more and a hexadecane contact angle of 60 ° or more.
<15> The laminate according to any one of <12> to <14>, wherein the surface energy of the antifouling layer is 16 mJ / m ² or less.
<16> The laminate according to any one of <12> to <15>, wherein the surface of the antifouling layer has a dynamic friction coefficient of 0.40 or less.
<17> The laminate according to any one of <12> to <16>, wherein the antifouling layer has an elastic recovery rate of 50% or more.
<18> The laminate according to <12>, wherein the water-repellent molecular structure is derived from a water-repellent monomer having fluorine.
<19> The antifouling layer is a cured product of the curable resin composition,
The curable resin composition is a laminate according to any one of <13> and <18>, containing the water-repellent monomer.
<20> The laminate according to <19>, wherein the curable resin composition contains a bifunctional or higher (meth) acrylate.
<21> The laminate according to <20>, wherein the bifunctional or higher functional (meth) acrylate has a ring structure.
<22> The laminate according to any one of <12> to <21>, wherein the resin layer has a multi-stage inclined surface like a Fresnel lens on a surface opposite to the antifouling layer side.
<23> The laminate according to any one of <12> to <13>, which is used for the Fresnel mirror according to any one of <1> to <11>.
<24> The method for producing a laminate according to <19>,
A process for producing a laminate comprising the steps of applying the curable resin composition containing the water repellent monomer onto the resin layer, curing the curable resin composition, and obtaining the cured product. Is the method.
<25> The method for producing a Fresnel mirror according to <11>,
Forming a multi-stage inclined surface like a Fresnel lens on the surface opposite to the viewing side of the resin layer;
Forming the light reflecting layer on the surface of the resin layer on which the inclined surface is formed;
It is a manufacturing method of the Fresnel mirror characterized by including.
<26> Before the step of forming the inclined surface, a curable resin composition containing a water-repellent monomer is applied onto the surface on the viewing side of the resin layer, and the curable resin composition is cured. It is a manufacturing method of the Fresnel mirror as described in said <25> including the process of obtaining the hardened | cured material which is the said antifouling layer.

According to the present invention, it is possible to provide a Fresnel mirror excellent in antifouling properties, a method for producing the same, a laminate used for the Fresnel mirror, and a method for producing the same.

FIG. 1 is a schematic sectional view of an example of the Fresnel mirror of the present invention. FIG. 2 is a plan view of the resin layer. FIG. 3 is a schematic cross-sectional view of another example of the Fresnel mirror of the present invention. FIG. 4A is a schematic cross-sectional view for explaining an example of a method for producing a Fresnel mirror of the present invention (part 1). FIG. 4B is a schematic cross-sectional view for explaining an example of the manufacturing method of the Fresnel mirror of the present invention (part 2). FIG. 4C is a schematic cross-sectional view for explaining an example of the manufacturing method of the Fresnel mirror of the present invention (part 3). FIG. 4D is a schematic cross-sectional view for explaining an example of the manufacturing method of the Fresnel mirror of the present invention (part 4). FIG. 4E is a schematic cross-sectional view for explaining an example of the manufacturing method of the Fresnel mirror of the present invention (part 5). FIG. 4F is a schematic cross-sectional view for explaining an example of the manufacturing method of the Fresnel mirror of the present invention (No. 6). FIG. 4G is a schematic cross-sectional view for explaining an example of the manufacturing method of the Fresnel mirror of the present invention (part 7).

(Fresnel mirror, laminate)
The Fresnel mirror of the present invention has at least an antifouling layer, preferably has a resin layer and a light reflecting layer, and further has other members such as a protective layer as necessary.
The antifouling layer is disposed on the viewing side surface of the Fresnel mirror.
The Fresnel mirror has excellent antifouling properties and can be easily wiped even if the surface is dirty. Therefore, the Fresnel mirror can easily recover good visibility even if the surface is soiled.

The laminated body of this invention has an antifouling layer and a resin layer, and also has another member as needed.
The laminate is used for a Fresnel mirror.
In the laminate before being used for the Fresnel mirror, the surface opposite to the antifouling layer may be a flat surface or may have a multi-stage inclined surface like a Fresnel lens. .

One aspect of the Fresnel mirror of the present invention is:
A laminate including an antifouling layer and a resin layer is provided.
The laminate has heat resistance.
Here, the heat resistance means that the laminate is placed on a hot plate set at 250 ° C. with the antifouling layer side up and held for 5 minutes, and then visually observed to prevent cracking or discoloration. means.

In one embodiment of the Fresnel mirror of the present invention,
The antifouling layer has a water-repellent molecular structure,
The water-repellent molecular structure is derived from a water-repellent monomer having fluorine,
The antifouling layer is a curable resin composition containing the water-repellent monomer (however, a polyisocyanate that is a diisocyanate trimer, a perfluoropolyether having active hydrogen, a silane compound containing active hydrogen, and Except for the case of containing a compound containing a carbon-carbon double bond obtained by reacting a compound having an active hydrogen containing a monomer having an active hydrogen and a carbon-carbon double bond).
The carbon-carbon double bond-containing compound can be obtained by reacting a polyisocyanate that is a trimer of diisocyanate with a compound having active hydrogen.
The compound having active hydrogen contains the following (A), (B) and (C).
(A) Perfluoropolyether having active hydrogen (B) Silane compound containing active hydrogen (C) Monomer having active hydrogen and carbon-carbon double bond

One embodiment of the laminate of the present invention has heat resistance.
Here, the heat resistance means that the laminate is placed on a hot plate set at 250 ° C. with the antifouling layer side up and held for 5 minutes, and then visually observed to prevent cracking or discoloration. means.

In one aspect of the laminate of the present invention,
The antifouling layer has a water-repellent molecular structure,
The water-repellent molecular structure is derived from a water-repellent monomer having fluorine,
The antifouling layer is a curable resin composition containing the water-repellent monomer (however, a polyisocyanate that is a diisocyanate trimer, a perfluoropolyether having active hydrogen, a silane compound containing active hydrogen, and Except for the case of containing a compound containing a carbon-carbon double bond obtained by reacting a compound having an active hydrogen containing a monomer having an active hydrogen and a carbon-carbon double bond).

A Fresnel mirror is a reflecting mirror in which a reflecting film is formed on a Fresnel lens.
The Fresnel lens is formed, for example, in a concentric ring-shaped inclined surface on one side of a transparent plastic plate in multiple stages, and the inclination angle is gradually increased from the concentric center to the radially outer side. . That is, the Fresnel lens is a lens formed by cutting the convex spherical surface or concave spherical surface of a lens into a large number of ring zones and rearranging them into a flat plate shape on a flat surface. When a metal film is formed on the inclined surface of the annular zone of such a Fresnel lens by plating, vapor deposition, or the like, a mirror having a convex mirror function or a concave mirror function can be obtained.

<Anti-fouling layer>
The antifouling layer has a water-repellent molecular structure. The water repellent molecular structure causes the antifouling layer to exhibit antifouling properties.
It is preferable that the water contact angle of the surface on the viewing side of the antifouling layer is 110 ° or more.
It is preferable that the hexadecane contact angle of the surface on the visual recognition side of the antifouling layer is 60 ° or more.
The surface energy of the surface on the viewing side of the antifouling layer is preferably 16 mJ / m ² or less.
The dynamic friction coefficient of the surface on the viewing side of the antifouling layer is preferably 0.40 or less.
The elastic recovery rate of the antifouling layer is preferably 50% or more.
The water-repellent molecular structure is preferably derived from a water-repellent monomer having fluorine.
The antifouling layer is a cured product of a curable resin composition, and the curable resin composition preferably contains the water repellent monomer.

<< Water contact angle >>
There is no restriction | limiting in particular as the water contact angle of the surface at the side of visual recognition of the said pollution protection layer, Although it can select suitably according to the objective, 110 degrees or more are preferable from the point which is more excellent in pollution resistance. There is no restriction | limiting in particular as an upper limit of the said water contact angle, According to the objective, it can select suitably, For example, the said water contact angle is 120 degrees or less, 130 degrees or less, etc. are mentioned.

The water contact angle can be measured under the following conditions using an automatic contact angle meter DM-501 manufactured by Kyowa Interface Chemical Co., Ltd.
・ Drip amount of distilled water: 2 μL
・ Measurement temperature: 25 ℃
The contact angle after 5 seconds from dropping water is measured by an ellipse fitting method at an arbitrary 10 locations on the test piece, and the average value is taken as the water contact angle.

<< Hexadecane contact angle >>
There is no restriction | limiting in particular as the hexadecane contact angle of the surface at the side of visual recognition of the said pollution protection layer, Although it can select suitably according to the objective, 60 degrees or more are preferable from the point which is more excellent in pollution resistance. There is no restriction | limiting in particular as an upper limit of the said hexadecane contact angle, According to the objective, it can select suitably, For example, the said hexadecane contact angle is 70 degrees or less, 80 degrees or less, etc. are mentioned.

The hexadecane contact angle can be measured under the following conditions using an automatic contact angle meter DM-501 manufactured by Kyowa Interface Chemical Co., Ltd.
・ Drop amount of hexadecane: 1 μL
・ Measurement temperature: 25 ℃
Hexadecane is dropped and the contact angle after 20 seconds has passed is measured by an ellipse fitting method at any 10 locations on the test piece, and the average value is taken as the hexadecane contact angle.

<< Surface energy >>
The surface energy of the surface on the visual recognition side of the antifouling layer is not particularly limited and can be appropriately selected according to the purpose. However, since the antifouling property is more excellent in that it is difficult to get dirt, 16 mJ / m It is preferable that it is ² or less. There is no restriction | limiting in particular as a lower limit of the said surface energy, According to the objective, it can select suitably, For example, 10 mJ / m < ² > or more, 12 mJ / m < ² > or more etc. are mentioned.

The surface energy can be calculated by the Kaelble-Uy method using the water contact angle and the hexadecane contact angle.
The Kaelble-Uy theoretical formula is a method for quantitatively determining the surface energy γ of a solid.

In the Kaelble-Uy theoretical formula, it is assumed that the surface energy γ is composed of a dispersion component γ ^d and a polar component γ ^p , and the total surface free energy γ is expressed by the following formula (1).
γ = γ ^d + γ ^p (1)

Further, when the surface energy of the liquid surface is represented by γ _L , the solid surface energy is represented by γ _S , and the contact angle is represented by θ, the following formula (2) is established.
γ _L (1 + cos θ) = 2√γ _S ^d γ _L ^d + 2√γ _S ^p γ _L ^p (2)

Therefore, the θ respective contact angles were measured using two liquid components of gamma ^L is ^known, γ _{S d,} γ _S is obtained by solving the simultaneous equations for gamma _S ^p.

<< Coefficient of dynamic friction >>
The dynamic friction coefficient of the surface on the viewing side of the antifouling layer is not particularly limited and can be appropriately selected according to the purpose. It is preferably 40 or less, more preferably 0.30 or less, and particularly preferably 0.20 or less. When the coefficient of dynamic friction is 0.40 or less, the wiping material has good sliding properties and can be easily wiped off even if dirt is attached. Moreover, when the said dynamic friction coefficient is small, the effect of releasing force will arise and the said pollution protection layer will not be damaged easily. There is no restriction | limiting in particular as a lower limit of the said dynamic friction coefficient, Although it can select suitably according to the objective, For example, the said dynamic friction coefficient is 0.05 or more.

The dynamic friction coefficient is obtained by the following method.
Measurement is performed using Triboster TS501 manufactured by Kyowa Interface Science Co., Ltd. BEMCOT (registered trademark) M-3II manufactured by Asahi Kasei Co., Ltd. is attached to the surface contactor with double-sided tape, measured 12 times with a measurement load of 50 g / cm ² , a measurement speed of 1.7 mm / s, and a measurement distance of 20 mm. It is a coefficient.

<< Elastic recovery factor >>
The elastic recovery rate of the antifouling layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50% or more and 60% or more in terms of excellent scratch resistance. More preferred. There is no restriction | limiting in particular as an upper limit of the said elastic recovery rate, Although it can select suitably according to the objective, The said elastic recovery rate may be 100% or less, for example.

The elastic recovery rate is obtained by the following method.
The elastic recovery rate of the test piece is measured under the following conditions using a PICODENTOR HM500 manufactured by Fischer Instruments.
Load: 1mN / 20s
Needle: Diamond cone with a surface angle of 136 ° Measured at any 10 points, and the average value is taken as the elastic recovery rate.

<< Average thickness >>
The average thickness of the antifouling layer is not particularly limited and may be appropriately selected depending on the purpose. For example, it may be 0.1 μm or more and 50 μm or less, or 0.5 μm or more and 50 μm or less. Or 0.5 μm or more and 30 μm or less.
The average thickness is obtained by, for example, the following method.
The thickness of the antifouling layer can be measured by observing the cross section with a field emission scanning electron microscope S-4700 (trade name; manufactured by Hitachi High-Technologies Corporation). Measurement is performed at any 10 points, and the average value is defined as the average thickness.
Moreover, you may measure with the film metrics Co., Ltd. F20 film thickness measurement system.

<< Curable resin composition >>
The antifouling layer is preferably a cured product of a curable resin composition.
The curable resin composition contains a water-repellent monomer having fluorine.
Examples of the curable resin composition include a thermosetting resin composition and an active energy ray curable resin composition, and an active energy ray curable resin composition is preferable.

<<< Active energy ray-curable resin composition >>>
The antifouling layer is preferably a cured product of an active energy ray curable resin composition.
The active energy ray-curable resin composition contains at least a water-repellent monomer, and further contains other components such as other monomers, a photopolymerization initiator, an ultraviolet absorber, a radical scavenger, and a solvent as necessary. To do.

-Water repellent monomer-
The water repellent monomer has fluorine.
The water repellent monomer has a water repellent molecular structure. Examples of the water-repellent molecular structure in the present invention include a structure having fluorine, and examples thereof include a fluoroalkyl structure and a perfluoropolyether structure.
When the active energy ray-curable resin composition contains the water-repellent monomer, the coefficient of dynamic friction of the antifouling layer can be reduced, and as a result, scratch resistance can be imparted to the antifouling layer.

The water repellent monomer has a (meth) acryloyl group. The number of the (meth) acryloyl groups in the water repellent monomer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 to 6.

The water-repellent monomer is preferably a (meth) acrylate containing a perfluoropolyether group, and the perfluoropolyether group is represented by — (O—CF ₂ CF ₂ ) — or — (O—CF ₂ CF ₂ CF _2). )-Or — (O—CF ₂ C (CF ₃ ) F) — is preferred.

The water-repellent monomer may be a commercially available product. Examples of the commercially available products include DAC-HP manufactured by Daikin Industries, Ltd., Fluorolink AD1700 manufactured by Solvay Specialty Polymers, Fluorolink MD700 manufactured by Solvay Specialty Polymers, CN4000 manufactured by Sartomer, and SHIN-ETSU SUBLYN manufactured by Shin-Etsu Chemical Co., Ltd. DIC Corporation RS Series, Kanto Denka Kogyo Co., Ltd. F Clear, Fluoro Technology Co., Ltd. Fluorosurf Co., Ltd., Daicel Ornex Co., Ltd. EBECRYL8110, and the like.

The molecular weight of the water repellent monomer is not particularly limited and can be appropriately selected according to the purpose.

The content of the water repellent monomer in the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose. On the other hand, 0.001 mass% or more and 5.0 mass% or less are preferable, 0.01 mass% or more and 5.0 mass% or less are more preferable, 0.01 mass% or more and 4.0 mass% or less are still more preferable. 0.04% by mass to 3.0% by mass is particularly preferable. If the content is less than 0.001% by mass, the antifouling property may be inferior. When the content exceeds 5.0% by mass, appearance deterioration (whitening, cloudiness) may occur in the antifouling layer.

-Other monomers-
The other monomer is not particularly limited as long as it is a monomer (active energy ray-curable component) other than the water-repellent monomer, and can be appropriately selected according to the purpose. For example, urethane (meth) acrylate, Examples include silicone (meth) acrylate and bifunctional or higher functional (meth) acrylate.
The urethane (meth) acrylate and the bifunctional or higher functional (meth) acrylate are used, for example, for adjusting the elastic recovery rate.
The silicone (meth) acrylate is used, for example, for adjusting the surface energy and the dynamic friction coefficient.

-Urethane (meth) acrylate-
Examples of the urethane (meth) acrylate include aliphatic urethane (meth) acrylate and aromatic urethane (meth) acrylate.
When the active energy ray-curable resin composition contains the water-repellent monomer, the dynamic friction coefficient of the antifouling layer can be reduced and scratch resistance can be imparted to the antifouling layer. When the curable resin composition contains the urethane (meth) acrylate, the coefficient of dynamic friction of the antifouling layer can be further reduced, and as a result, the flaw resistance of the antifouling layer can be further improved. .

The urethane (meth) acrylate refers to a material having a urethane bond and a (meth) acryloyl group in one molecule, and such a material can be used without any particular limitation.

The urethane (meth) acrylate is obtained, for example, by a reaction between a hydroxy compound having at least one (meth) acryloyl group and an isocyanate.
Examples of the isocyanate include polyisocyanate.

The aliphatic urethane (meth) acrylate is obtained, for example, by a reaction between a hydroxy compound having at least one (meth) acryloyl group and an aliphatic isocyanate. Examples of the aliphatic isocyanate include aliphatic diisocyanate and aliphatic triisocyanate.
The aromatic urethane (meth) acrylate is obtained, for example, by a reaction between a hydroxy compound having at least one (meth) acryloyl group and an aromatic isocyanate. Examples of the aromatic isocyanate include aromatic diisocyanate and aromatic triisocyanate.

There is no restriction | limiting in particular as content of the said urethane (meth) acrylate in the said active energy ray curable resin composition, Although it can select suitably according to the objective, The non-volatile property of the said active energy ray curable resin composition The content is preferably 10% by mass or more and 90% by mass or less, more preferably 15% by mass or more and 85% by mass or less, and particularly preferably 15% by mass or more and 60% by mass or less.

--- Silicone (meth) acrylate--
The silicone (meth) acrylate is a (meth) acrylate having a silicone skeleton.

There is no restriction | limiting in particular as content of the said silicone (meth) acrylate in the said active energy ray-curable resin composition, Although it can select suitably according to the objective, The non-volatile property of the said active energy ray-curable resin composition 0.001 mass% or more and 5.0 mass% or less are preferable with respect to a minute.

--2 (meth) acrylates with higher functionality--
The bifunctional or higher functional (meth) acrylate is not particularly limited as long as it is a material having two or more (meth) acryloyl groups in one molecule, and can be appropriately selected according to the purpose.
When the active energy ray-curable resin composition contains the bifunctional or higher functional (meth) acrylate, the laminate can have excellent press resistance and heat resistance.

The number of (meth) acryloyl groups in the bifunctional or higher (meth) acrylate is not particularly limited as long as it is 2 or more, and can be appropriately selected according to the purpose. Is more preferable, and 2 to 6 is particularly preferable.

Examples of the bifunctional or higher functional (meth) acrylate include bifunctional (meth) acrylate, trifunctional (meth) acrylate, and tetrafunctional (meth) acrylate.

Examples of the tri- or more functional (meth) acrylates include dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, glycerin ethoxytri (meth) acrylate, Glycerin propoxytri (meth) acrylate, isocyanuric acid ethoxytri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Etc.
Here, as alkoxy, ethoxy, propoxy, etc. are mentioned, for example.

The bifunctional or higher (meth) acrylate preferably has a ring structure. Examples of the ring structure include an alicyclic structure, an aromatic structure, a heterocyclic structure, a polycyclic structure, and an isocyanuric ring structure.
Examples of the bifunctional or higher functional (meth) acrylate having the ring structure include tricyclodecane dimethanol di (meth) acrylate, isocyanuric acid ethoxydi (meth) acrylate [for example, isocyanuric acid EO-modified diacrylate] and the like. It is done.
Here, the ring structure gives hardness to the cured product (antifouling layer) of the active energy ray-curable resin composition. This hardness appears, for example, in the glass transition temperature of the antifouling layer. The glass transition temperature of the antifouling layer is preferably, for example, 130 ° C. or higher. A high glass transition temperature contributes to the antifouling layer obtaining excellent scratch resistance. Even if the glass transition temperature is high, if the elastic recovery rate is low, excellent scratch resistance cannot be obtained.

The content of the bifunctional or higher functional (meth) acrylate in the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose. 10 mass% or more and 99 mass% or less are preferable with respect to the non volatile matter of a thing, and 15 mass% or more and 99 mass% or less are more preferable.
The content of the bifunctional or higher functional (meth) acrylate in the active energy ray-curable resin composition is 10 mass when the active energy ray-curable resin composition contains the urethane (meth) acrylate. % To 90% by mass is preferable, and 15% to 85% by mass is more preferable.
The content of the bifunctional or higher functional (meth) acrylate having the ring structure in the active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose. 10 mass% or more and 99 mass% or less are preferable with respect to the non volatile matter of a wire curable resin composition, and 15 mass% or more and 90 mass% or less are more preferable.

Here, in the present invention, the water repellent monomer, the urethane (meth) acrylate, the silicone (meth) acrylate, and the bifunctional or higher functional (meth) acrylate are positioned as different materials in the following points. .
A monomer having a fluorine atom belongs to the water-repellent monomer even if it is bifunctional or higher.
The monomer having a fluorine atom belongs to the water-repellent monomer even if it has a urethane bond.
The monomer having a fluorine atom belongs to the water-repellent monomer even if it has a silicone skeleton.
A monomer having a silicone skeleton belongs to the silicone (meth) acrylate even if it is bifunctional or higher.
A monomer having a silicone skeleton belongs to the silicone (meth) acrylate even if it has a urethane bond.
A monomer having no fluorine atom and no silicone skeleton but having a urethane bond belongs to the urethane (meth) acrylate even if it is bifunctional or higher.
A monomer that does not have a fluorine atom, a silicone skeleton, and a urethane bond but is bifunctional or higher belongs to the bifunctional or higher (meth) acrylate.

-Photopolymerization initiator-
Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photoacid generator, a bisazide compound, hexamethoxymethylmelamine, and tetramethoxyglycolyl.
There is no restriction | limiting in particular as said radical photopolymerization initiator, According to the objective, it can select suitably, For example, the following compounds are mentioned.
1-hydroxy-cyclohexyl-phenyl-ketone 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one 2,2-dimethoxy-1,2-diphenylethane-1-one • 2-hydroxy-2-methyl-1-phenyl-propan-1-one • 1- [4- (2-hydroxyethoxy) -phenyl]- 2-hydroxy-2-methyl-1-propan-1-one oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl Ester mixture 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide

The photopolymerization initiator preferably does not contain a nitrogen atom as a constituent element from the viewpoint of preventing yellowing in appearance.
On the other hand, the photopolymerization initiator may contain only C, H, and O as constituent elements, or only C, H, P, and O as constituent elements from the viewpoint of preventing yellowing in appearance. preferable.

There is no restriction | limiting in particular as content of the said photoinitiator in the said active energy ray curable resin composition, Although it can select suitably according to the objective, The non-volatile content of the said active energy ray curable resin composition Is preferably 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, and particularly preferably 1% by mass to 5% by mass.

-UV absorber-
Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, triazine compounds, benzoate compounds, benzoxazinone compounds, cyanoacrylate compounds, benzoxazole compounds, merocyanine compounds, salicylate compounds, Examples include formamidine compounds and oxanilide compounds.

The ultraviolet absorber may be a commercially available product. Examples of the commercially available products include the Tinuvin series, the Chimassorb series, the Uvinul series manufactured by BASF, the Adeka Stub LA series manufactured by ADEKA Corporation, the Chemisorb series manufactured by Chemipro Kasei Co., Ltd., and the SEESORB series manufactured by Sipro Kasei Co., Ltd. Examples include benzotriazole-based compounds.

The content of the ultraviolet absorber in the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose.

-Radical scavenger-
Examples of the radical scavenger include amine compounds, phenol compounds, and benzoate compounds.

The radical scavenger may be a commercially available product. Examples of the commercially available products include: Tinufin series manufactured by BASF, Chimassorb series, Adeka stab manufactured by ADEKA, LA series, Chemisorb series manufactured by Chemipro Kasei Co., Ltd., Chemistab series, Cheminox series, SEENOX series manufactured by Sipro Kasei Co., Ltd. Is mentioned.

The content of the radical scavenger in the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose.

-solvent-
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, an organic solvent is mentioned.
Examples of the organic solvent include aromatic solvents, alcohol solvents, ester solvents, ketone solvents, glycol ether solvents, glycol ether ester solvents, chlorine solvents, ether solvents, N-methylpyrrolidone, dimethyl Examples include formamide, dimethyl sulfoxide, dimethylacetamide, and the like.

As the solvent, a solvent having a boiling point of 80 ° C. or higher is preferable from the viewpoint of obtaining an antifouling layer having a better appearance.
Examples of the solvent having a boiling point of 80 ° C. or higher include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1,3-butanediol, 1,4-butanediol, 2-ethyl-1-hexanol, normal propyl acetate, isopropyl acetate, butyl acetate, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, diacetone alcohol, propylene glycol monomethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, 1,4-dioxane, Examples thereof include methyl carbitol, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, and butyl carbitol acetate.

The content of the solvent in the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose.

The active energy ray-curable resin composition is cured when irradiated with active energy rays. There is no restriction | limiting in particular as said active energy ray, According to the objective, it can select suitably, For example, an electron beam, an ultraviolet-ray, infrared rays, a laser beam, visible light, ionizing radiation (X ray, alpha ray, beta ray, gamma) Wire, etc.), microwave, high frequency and the like.

<Resin layer>
There is no restriction | limiting in particular as a material of the said resin layer, According to the objective, it can select suitably, For example, a triacetyl cellulose (TAC), polyester (TPEE), a polyethylene terephthalate (PET), a polyethylene naphthalate (PEN) , Polyimide (PI), polyamide (PA), aramid, polyethylene (PE), polyacrylate, polyethersulfone, polysulfone, polypropylene (PP), polystyrene, diacetylcellulose, polyvinyl chloride, acrylic resin (PMMA), polycarbonate ( PC), epoxy resin, urea resin, urethane resin, melamine resin, phenol resin, acrylonitrile / butadiene / styrene copolymer, cycloolefin polymer (COP), cycloolefin copolymer (COC) PC / PMMA laminate, such as rubber additives PMMA and the like.
The resin layer may have, for example, a single layer structure made of the above material or a laminated structure made of a plurality of the above materials.

The resin layer has transparency.

The average thickness of the resin layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 25 μm to 5 mm, and more preferably 500 μm to 5 mm.

The resin layer usually has a Fresnel lens-like multi-level inclined surface on the surface opposite to the viewing side.

<Light reflection layer>
The light reflecting layer is not particularly limited as long as it is a layer having light reflectivity arranged on the surface having the inclined surface of the resin layer, and can be appropriately selected according to the purpose. For example, examples of the material include metals such as gold, aluminum, platinum, chromium, and silver.
The light reflection layer can be formed, for example, by arranging the metal in a layered manner by plating or vapor deposition on the surface of the resin layer having the inclined surface.
The light reflecting layer may be, for example, a dielectric deposited multilayer film.

The average thickness of the light reflection layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 10 nm to 1,000 nm.

<Protective layer>
The protective layer is not particularly limited as long as it is a layer disposed on the surface of the light reflecting layer opposite to the resin layer, and can be appropriately selected according to the purpose.
The protective layer protects the metal layer from oxidation and corrosion due to contact with air and water.

There is no restriction | limiting in particular as a formation method of the said protective layer, According to the objective, it can select suitably, For example, by apply | coating a colored paint on the surface on the opposite side to the said resin layer side of the said light reflection layer. Can be formed.

The average thickness of the protective layer is not particularly limited and can be appropriately selected depending on the purpose.

Here, an example of the Fresnel mirror will be described.

FIG. 1 is a schematic sectional view of an example of the Fresnel mirror of the present invention. The upper side in FIG. 1 is the viewing side.
FIG. 2 is a plan view of the resin layer.
The Fresnel mirror in FIG. 1 has an antifouling layer 1, a resin layer 2, and a light reflecting layer 3.
The antifouling layer 1 is disposed on the surface on the viewing side.
On the surface of the resin layer 2 opposite to the viewing side, a large number of annular inclined surfaces 2a are formed in multiple stages and concentrically in the form of a Fresnel lens as shown in FIG. In FIG. 1 and FIG. 2, for easy understanding, the multi-step inclined surfaces 2a are shown with a rough pitch, but are generally formed with a density of about 2 to 10 steps per 1 mm width. A light reflecting layer 3 is formed on the inclined surface 2a formed in multiple stages.

In the example of FIG. 1, the light reflecting layer 3 (inclined surface 2a) serving as a reflecting surface is inclined outward with respect to the center of the concentric circle so that it functions as a convex mirror. It is also possible to function as a concave mirror by inclining the surface 2a) inward with respect to the concentric circle center.

FIG. 3 is a schematic cross-sectional view of another example of the Fresnel mirror of the present invention.
The Fresnel mirror of FIG. 3 includes an antifouling layer 1, a resin layer 2, a light reflecting layer 3, and a protective layer 4.
The antifouling layer 1 is disposed on the surface on the viewing side.
On the surface of the resin layer 2 opposite to the viewing side, a large number of annular inclined surfaces 2a are formed in multiple stages and concentrically in the form of a Fresnel lens as shown in FIG. A light reflecting layer 3 is formed on the inclined surface 2a formed in multiple stages.
The protective layer 4 is disposed so as to be in contact with the surface of the light reflecting layer 3 opposite to the viewing side. The protective layer 4 embeds a multi-stage uneven surface.

(Laminate manufacturing method)
The manufacturing method of the laminated body of this invention includes the process of obtaining hardened | cured material, and also includes another process as needed.
The manufacturing method of the said laminated body is a method of manufacturing the said laminated body of this invention.

<Step of obtaining a cured product>
The process for obtaining the cured product is not particularly limited as long as it is a process for obtaining a cured product by applying a curable resin composition containing a water repellent monomer onto a resin layer and curing the curable resin composition. It can be appropriately selected depending on the purpose.

As said curable resin composition, the said curable resin composition illustrated in description of the said Fresnel mirror of this invention is mentioned.
Examples of the resin layer include the resin layer exemplified in the description of the Fresnel mirror of the present invention.

The method for applying the curable resin composition onto the resin layer is not particularly limited and may be appropriately selected depending on the purpose. For example, wire bar coating, blade coating, spin coating, reverse roll coating, Examples include die coating, spray coating, roll coating, gravure coating, micro gravure coating, lip coating, air knife coating, curtain coating, comma coating method, and dipping method.

The method for curing the curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose, but the curable resin composition is an active energy ray curable resin composition, A method in which the active energy ray-curable resin composition is irradiated with an active energy ray and cured is preferable. There is no restriction | limiting in particular as said active energy ray, According to the objective, it can select suitably, For example, an electron beam, an ultraviolet-ray, infrared rays, a laser beam, visible light, ionizing radiation (X ray, alpha ray, beta ray, gamma) Wire, etc.), microwave, high frequency and the like.

The curing is a step of forming the antifouling layer by irradiating an uncured layer formed from the active energy ray-curable resin composition with an active energy ray in an atmosphere having an oxygen concentration of less than 1% by volume. Preferably there is.
Examples of the atmosphere having an oxygen concentration of less than 1% by volume include an inert gas atmosphere such as a nitrogen atmosphere.

<Other processes>
As said other process, the process of forming the inclined surface mentioned later etc. are mentioned.

(Fresnel mirror manufacturing method)
The method for producing a Fresnel mirror of the present invention includes at least a step of forming an inclined surface and a step of forming a light reflecting layer, and further includes other steps as necessary.
The method for producing the Fresnel mirror is a method for producing the Fresnel mirror of the present invention.

<Step of forming an inclined surface>
The step of forming the inclined surface is not particularly limited as long as it is a step of forming a Fresnel lens-like multi-step inclined surface on the surface opposite to the viewing side of the resin layer, and is appropriately selected according to the purpose. For example, there is a method in which the resin layer is pressed against a predetermined mold heated to a temperature higher than the softening temperature of the resin layer to form a Fresnel lens-like multi-step inclined surface.

<Process for forming light reflecting layer>
The step of forming the light reflecting layer is not particularly limited as long as it is a step of forming the light reflecting layer on the surface of the resin layer on which the inclined surface is formed, and is appropriately selected according to the purpose. For example, a method of forming a light reflection layer, which is a metal layer, by plating, vapor deposition, or the like on the surface of the resin layer on which the inclined surface is formed may be mentioned.

<< Other processes >>
As said other process, the process of obtaining hardened | cured material is mentioned, for example.

<<< Step of obtaining a cured product >>>
As the step of obtaining the cured product, before the step of forming the inclined surface, a curable resin composition containing a water-repellent monomer is applied on the visual side surface of the resin layer, and the curable resin is obtained. If it is the process of hardening a composition and obtaining hardened | cured material, there will be no restriction | limiting in particular, According to the objective, it can select suitably, For example, the said hardened | cured material illustrated in the manufacturing method of the said laminated body of this invention is obtained. The process etc. are mentioned.

Here, an example of the manufacturing method of the Fresnel mirror of this invention is demonstrated using figures.
4A to 4G are schematic cross-sectional views for explaining an example of the manufacturing method of the Fresnel mirror of the present invention.
First, the flat resin layer 2 is prepared (FIG. 4A).
Next, the antifouling layer 1 is formed on one surface of the resin layer 2 to produce a laminate (FIG. 4B).
Next, a mold 11 for providing a Fresnel lens-like shape on the other surface of the resin layer 2 is prepared (FIG. 4C).
Next, the heated mold 11 is pressed against the surface on the resin layer 2 side of the laminate (FIG. 4D), and a Fresnel lens-like multi-step inclined surface 2a is formed on one surface of the resin layer 2 (FIG. 4). 4E).
Next, the light reflection layer 3 is formed on the surface of the resin layer 2 where the inclined surface 2a is formed (FIG. 4F).
Next, the protective layer 4 is formed on the light reflecting layer 3.
As described above, a Fresnel mirror is obtained.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Water contact angle>
The water contact angle was measured using an automatic contact angle meter DM-501 manufactured by Kyowa Interface Chemical Co., Ltd. under the following conditions.
・ Drip amount of distilled water: 2 μL
・ Measurement temperature: 25 ℃
The contact angle after 5 seconds from dropping of water was measured by an ellipse fitting method at any 10 locations on the test piece, and the average value was taken as the water contact angle.

<Hexadecane contact angle>
The hexadecane contact angle was measured using an automatic contact angle meter DM-501 manufactured by Kyowa Interface Chemical Co., Ltd. under the following conditions.
・ Drop amount of hexadecane: 1 μL
・ Measurement temperature: 25 ℃
Hexadecane was dropped and the contact angle after 20 seconds was measured by an ellipse fitting method at an arbitrary 10 locations on the test piece, and the average value was defined as the hexadecane contact angle.

<Surface energy>
The surface energy was calculated by the Kaelble-Uy method using the water contact angle and the hexadecane contact angle.

<Dynamic friction coefficient>
It measured using Triboster TS501 by Kyowa Interface Science Co., Ltd. BEMCOT (registered trademark) M-3II manufactured by Asahi Kasei Co., Ltd. was attached to the surface contactor with double-sided tape and measured 12 times with a measurement load of 50 g / cm ² , a measurement speed of 1.7 mm / s, and a measurement distance of 20 mm. Coefficient.

<Elastic recovery rate>
The elastic recovery rate of the test piece was measured under the following conditions using a PICODETOR HM500 manufactured by Fischer Instruments.
Load: 1mN / 20s
Needle: Diamond cone with a surface angle of 136 ° Measured at any 10 points, and the average value was taken as the elastic recovery rate.

<Adhesion and removal of oil-based magic (antifouling)>
The specimen was soiled with Sharpie PROFESSIONAL (black oily magic, trade name, manufactured by Newell Rubbermaid). This was wiped dry with tissue paper (Daiou Paper Co., Ltd., Erière) 10 times and then visually observed and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
○: Fouling 2 to 5 times to remove the dirt.
Δ: Weakly repels. Dirt disappeared after 6-10 wiping.
X: Dirt remained even after wiping 10 times, and the function of the mirror was impaired.

<Scratch resistance>
The test piece was rubbed 3,600 times with a bonster steel wool # 0000 manufactured by Nippon Steel Wool Co., Ltd. under a load of 1,500 gf / 4 cm ² and then visually observed and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
○: No change.
Δ: Slightly damaged but no problem with mirror function.
×: Many scratches occurred and the surface became white and the mirror function was lost.

<Press resistance>
After the press work described later, the mirror was visually confirmed, and the press resistance was evaluated according to the following evaluation criteria.
[Evaluation criteria]
○: No cracks or cracks, and image clarity was maintained.
X: Image clarity was deteriorated by cracking, cracking or coloring.

<Heat resistance>
The following tests were performed on the laminate (resin base material on which the antifouling layer was formed) before pressing.
The laminate was placed on a hot plate set at 250 ° C. with the antifouling layer side up and held for 5 minutes, then visually observed and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
○: No cracking or discoloration.
X: Cracked or discolored.

<Glass transition temperature>
The glass transition temperature of the antifouling layer was determined by differential scanning calorimetry. Specifically, it was measured using a DSC7000X manufactured by Hitachi High-Technologies Corporation under a nitrogen atmosphere at a temperature rising condition of 10 ° C. per minute, and was calculated from the DSC curve by a tangent method. As a measurement sample, a 0.5 mm-thick test piece cured by irradiation with a metal halide lamp in a nitrogen atmosphere so that the integrated light quantity at 365 nm was 500 mJ / cm ² was used.

(Example 1)
<Manufacture of Fresnel mirror>
DF02PU (PMMA / PC laminated sheet, thickness = 0.3 mm) manufactured by Mitsubishi Gas Chemical Co., Ltd. was used as the resin base material.
The active energy ray-curable resin composition shown in Table 1 was applied to the PMMA side of the resin base material so that the film thickness after drying and curing was the value shown in Table 1. After coating, it was dried in an oven at 80 ° C. for 3 minutes. The antifouling layer was cured by irradiating with ultraviolet rays at a dose of 500 mJ / cm ² in a nitrogen atmosphere (oxygen concentration of 500 ppm or less) using a metal halide lamp.

Next, the following press work was performed.
-Press working-
Next, Fresnel lens-like annular grooves were formed on the PC (polycarbonate) side by press working using a mold in which the resin base material on which the antifouling layer was formed was heated to 250 ° C. Then, after cooling to 60 degrees C or less, it removed from the metal mold | die.

Next, a metal was deposited on the surface of the annular groove on the PC side to form a light reflecting layer.
Next, a protective layer was formed on the surface of the light reflecting layer with a black lacquer spray to obtain a super-fouling Fresnel mirror.

The super antifouling Fresnel mirror obtained was subjected to the above evaluations. The results are shown in Table 1.

(Examples 2 to 6)
In Example 1, a super antifouling Fresnel mirror was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition was changed to the active energy ray-curable resin composition shown in Table 1. .

The super antifouling Fresnel mirror obtained was subjected to the above evaluations. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, the Fresnel mirror was obtained like Example 1 except having changed the active energy ray-curable resin composition into the active energy ray-curable resin composition shown in Table 1.

The obtained Fresnel mirror was subjected to each of the above evaluations. The results are shown in Table 1.

(Comparative Example 2)
About the commercially available Fresnel mirror for back confirmation, it used for said each evaluation (however, press tolerance and heat resistance are remove | excluded). The results are shown in Table 1.

In Table 1, the unit of the content of each component of the active energy ray-curable resin composition is part by mass.
Details of the materials listed in Table 1 are as follows.
In the comparative example, “−” indicates that evaluation was not performed.

DAC-HP: Terminal (meth) acrylic modified perfluoropolyether (Daikin Industries, Ltd.)
KY-1203: Perfluoropolyether-containing acrylate (Shin-Etsu Chemical Co., Ltd.)
MU9500: aliphatic urethane acrylate oligomer (functional group number: 10, MIWON)
CN975: Aromatic urethane acrylate oligoomer (functional group number 6: SARTOMER)
A-GLY-20E: Ethoxylated glycerin triacrylate (Shin Nakamura Kogyo Co., Ltd.)
SR9035: Ethoxylated trimethylolpropane triacrylate (SARTOMER)
A-TMMT: Pentaerythritol tetraacrylate (Shin Nakamura Chemical Co., Ltd.)
EBECRYL130: Tricyclodecane dimethanol diacrylate (Daicel Ornex Co., Ltd.)
EBECRYL40: Pentaerythritol alkoxytetraacrylate (Daicel Ornex Co., Ltd.)
M-215: Isocyanuric acid EO-modified diacrylate (Toagosei Co., Ltd.)
Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone (BASF)
・ PGM: Propylene glycol monomethyl ether

The details of the bifunctional or higher acrylate monomer [bifunctional or higher (meth) acrylate] shown in Table 1 are as follows.

The Fresnel mirrors of Examples 1 to 6 were excellent in all of antifouling property, scratch resistance, press resistance and heat resistance.
From the evaluation results of scratch resistance in Examples 1 to 6, it was found that the lower the dynamic friction coefficient, the better the scratch resistance.
The Fresnel mirrors of Examples 3 to 6 were more excellent in scratch resistance because the coefficient of dynamic friction was 0.20 or less.
In addition, in Examples 3 to 6, the glass transition temperature is high. This is also one of the reasons why the scratch resistance is excellent.
In addition, Examples 3 to 5 using a bifunctional or higher functional (meth) acrylate having a ring structure had excellent elastic recovery (60% or higher) and a high glass transition temperature. It was excellent in Examples 1-6. When the elastic recovery rate is low (less than 60%), deformation tends to be difficult to return to, and the scratch resistance is reduced as compared with the case where the elastic recovery rate is 60% or more.

In Comparative Example 1, since the water contact angle and the hexadecane contact angle were low, the surface energy was larger than 16 mJ / m ^{2 and} the adhesion of the oily magic was inferior. In addition, the coefficient of dynamic friction was greater than 0.40 and the removability was poor.
In Comparative Example 2, the dynamic friction coefficient was 0.40 or less, but the elastic recovery rate was less than 50%, and the scratch resistance was insufficient.

The Fresnel mirror of the present invention has the characteristics of a Fresnel mirror that can be reduced in thickness as compared with a conventional convex mirror, and has excellent antifouling properties, so ATM (automatic teller machine) It can be installed in a wide range of convenience stores, roadways, office buildings, factories, railways, airplanes, etc., and used as a blind spot confirmation mirror and a rear confirmation mirror.

DESCRIPTION OF SYMBOLS 1 Antifouling layer 2 Resin layer 2a Inclined surface 3 Metal layer 4 Protective layer

Claims (26)

1. Having a laminate comprising an antifouling layer and a resin layer;
   The laminate has heat resistance,
   The Fresnel mirror characterized in that the antifouling layer is disposed on the surface on the viewing side and has a water-repellent molecular structure.
   Here, the heat resistance means that the laminate is placed on a hot plate set at 250 ° C. with the antifouling layer side up and held for 5 minutes, and then visually observed to prevent cracking or discoloration. means.
2. It has an antifouling layer on the surface on the viewing side,
   The antifouling layer has a water-repellent molecular structure;
   The water repellent molecular structure is derived from a water repellent monomer having fluorine,
   The antifouling layer is a curable resin composition containing the water-repellent monomer (however, a polyisocyanate which is a diisocyanate trimer, a perfluoropolyether having active hydrogen, a silane compound containing active hydrogen, and Except for the case of containing a carbon-carbon double bond-containing compound obtained by reacting a compound having an active hydrogen containing a monomer having an active hydrogen and a carbon-carbon double bond). Fresnel mirror characterized by.
3. The Fresnel mirror according to any one of claims 1 to 2, wherein a water contact angle of a surface on the viewing side of the antifouling layer is 110 ° or more and a hexadecane contact angle is 60 ° or more.
4. The Fresnel mirror according to any one of claims 1 to 3, wherein the surface energy of the surface on the viewing side of the antifouling layer is 16 mJ / m ² or less.
5. The Fresnel mirror according to any one of claims 1 to 4, wherein a dynamic friction coefficient of a surface on the viewing side of the antifouling layer is 0.40 or less.
6. The Fresnel mirror according to any one of claims 1 to 5, wherein an elastic recovery rate of the antifouling layer is 50% or more.
7. The Fresnel mirror according to claim 1, wherein the water-repellent molecular structure is derived from a water-repellent monomer having fluorine.
8. The antifouling layer is a cured product of a curable resin composition,
   The Fresnel mirror according to claim 2, wherein the curable resin composition contains the water-repellent monomer.
9. The Fresnel mirror according to claim 8, wherein the curable resin composition contains a bifunctional or higher functional (meth) acrylate.
10. The Fresnel mirror according to claim 9, wherein the bifunctional or higher functional (meth) acrylate has a ring structure.
11. The antifouling layer;
    A resin layer having a multi-step inclined surface like a Fresnel lens on the surface opposite to the viewing side;
    A light reflecting layer disposed on a surface of the resin layer having the inclined surface;
    The Fresnel mirror according to claim 1, comprising:
12. It is a laminate that is used for Fresnel mirrors and has heat resistance,
    An antifouling layer having a water-repellent molecular structure;
    A resin layer;
    A laminate characterized by comprising:
    Here, the heat resistance means that the laminate is placed on a hot plate set at 250 ° C. with the antifouling layer side up and held for 5 minutes, and then visually observed to prevent cracking or discoloration. means.
13. A laminate used for a Fresnel mirror,
    An antifouling layer having a water-repellent molecular structure;
    A resin layer;
    Have
    The water repellent molecular structure is derived from a water repellent monomer having fluorine,
    The antifouling layer is a curable resin composition containing the water-repellent monomer (however, a polyisocyanate which is a diisocyanate trimer, a perfluoropolyether having active hydrogen, a silane compound containing active hydrogen, and Except for the case of containing a carbon-carbon double bond-containing compound obtained by reacting a compound having an active hydrogen containing a monomer having an active hydrogen and a carbon-carbon double bond). A laminate characterized by the following.
14. The laminate according to any one of claims 12 to 13, wherein the surface of the antifouling layer has a water contact angle of 110 ° or more and a hexadecane contact angle of 60 ° or more.
15. The laminate according to any one of claims 12 to 14, wherein the surface energy of the antifouling layer is 16 mJ / m ² or less.
16. The laminate according to any one of claims 12 to 15, wherein the surface of the antifouling layer has a dynamic friction coefficient of 0.40 or less.
17. The laminate according to any one of claims 12 to 16, wherein an elastic recovery rate of the antifouling layer is 50% or more.
18. The laminate according to claim 12, wherein the water-repellent molecular structure is derived from a water-repellent monomer having fluorine.
19. The antifouling layer is a cured product of a curable resin composition,
    The laminate according to any one of claims 13 and 18, wherein the curable resin composition contains the water-repellent monomer.
20. The laminate according to claim 19, wherein the curable resin composition contains a bifunctional or higher functional (meth) acrylate.
21. The laminate according to claim 20, wherein the bifunctional or higher functional (meth) acrylate has a ring structure.
22. The laminate according to any one of claims 12 to 21, wherein the resin layer has a Fresnel lens-like multi-stage inclined surface on a surface opposite to the antifouling layer side.
23. The laminate according to any one of claims 12 to 13, which is used for the Fresnel mirror according to any one of claims 1 to 11.
24. It is a manufacturing method of the layered product according to claim 19,
    A process for producing a laminate comprising the steps of applying the curable resin composition containing the water repellent monomer onto the resin layer, curing the curable resin composition, and obtaining the cured product. Method.
25. It is a manufacturing method of the Fresnel mirror of Claim 11,
    Forming a multi-stage inclined surface like a Fresnel lens on the surface opposite to the viewing side of the resin layer;
    Forming the light reflecting layer on the surface of the resin layer on which the inclined surface is formed;
    The manufacturing method of the Fresnel mirror characterized by including.
26. Prior to the step of forming the inclined surface, a curable resin composition containing a water-repellent monomer is applied onto the surface of the resin layer on the viewing side, the curable resin composition is cured, and the antifouling agent is applied. The manufacturing method of the Fresnel mirror of Claim 25 including the process of obtaining the hardened | cured material which is a layer.

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