JP2019059234A - Active energy ray curable resin composition, laminate, method for manufacturing the same, and article - Google Patents

Abstract

To provide a laminate, etc., having excellent visibility of an edge portion thereof, the laminate including a primer layer and having at least one of an antifogging property and an antifouling property.SOLUTION: A laminate includes a substrate, a primer layer on the substrate, and a functional layer on the primer layer, the functional layer having a function of at least one of an antifogging property and an antifouling property. A surface of an edge portion of the laminate at a side of the functional layer has a projected portion having an apex portion formed along an edge side of the edge portion. On a cross-section orthogonal to a direction of the edge side and a planar direction of the surface, a height of the projected portion is 10 μm or less, a width of the projected portion is 15 mm or less, and a length between the edge side and the apex portion is 5.0 mm or less.SELECTED DRAWING: Figure 1

Description

  The present invention is a laminate having at least one of anti-fogging property and anti-staining property that can be used in a wide range of applications such as architectural applications, industrial applications, automotive applications, optical applications, solar cell panels, etc. And an active energy ray curable resin composition applicable to the formation of a primer layer of the laminate.

In order to decorate and protect the surface of various articles, a resin film, glass or the like is attached to the surface.
However, the visibility of the article and the appearance may deteriorate due to the fact that the resin film, glass, etc. that decorate and protect the surface of the article become cloudy.
Therefore, in order to prevent the deterioration of the visibility and the aesthetics of such an article, the resin film and the glass are subjected to antifogging treatment or antifouling treatment.

For example, an electron beam-curable hard coat sheet having antifogging properties and antifouling properties and having a specific composition has been proposed (see, for example, Patent Document 1).
In addition, for example, an antifogging laminate having an antifogging layer has been proposed (see, for example, Patent Document 2).

  Generally, the method for producing these laminates applies a resin composition having antifogging properties or antifouling properties onto a substrate, and then cures the functional layer having antifogging properties or antifouling properties. Is a method of obtaining a laminate. At this time, a primer layer may be formed between the substrate and the functional layer in order to improve the adhesion between the substrate and the functional layer. In that case, there is a problem that the transmitted image or the reflected image of the laminate is distorted at the end of the laminate, and the visibility of the images is reduced.

Patent No. 3760669 gazette JP 2017-81148 A

  An object of the present invention is to solve the above-mentioned problems in the prior art and to achieve the following objects. That is, the present invention is a laminate having at least one of antifogging properties and antifouling properties, and provided with a primer layer, which is also excellent in the visibility of the end, and the method for producing the same An object of the present invention is to provide an active energy ray curable resin composition applicable to the formation of the primer layer of the laminate and an article using the same.

The means for solving the problems are as follows. That is,
<1> A laminate having a substrate, a primer layer on the substrate, and a functional layer having at least one of antifogging and antifouling functions on the primer layer,
The surface on the functional layer side of the end portion of the laminate has a convex portion having a top side portion along the end side of the end portion,
The height of the protrusion is 10 μm or less, the width of the protrusion is 15 mm or less, and the edge and the top side in a cross section orthogonal to the direction of the edge and the surface direction of the surface And a length between them is 5.0 mm or less.
<2> The layered product according to <1>, wherein a height of the convex portion is 1 μm to 10 μm.
<3> The laminate according to any one of <1> to <2>, wherein the contact angle of pure water on the surface of the functional layer is 80 ° or more, and the contact angle of hexadecane is 35 ° or more. .
<4> The laminate according to any one of <1> to <3>, wherein the average thickness of the primer layer is 0.5 μm to 5 μm.
The average thickness of the <5> above-mentioned functional layer is a layered product in any one of the above-mentioned <1> to <4> which is 10 micrometers or more.
<6> The laminate according to any one of <1> to <5>, wherein a dynamic friction coefficient of the functional layer is 0.40 or less.
<7> The primer layer is a cured product of an active energy ray-curable resin composition,
The active energy ray curable resin composition is a laminate according to any one of <1> to <6>, which contains a surfactant.
<8> The laminate according to <7>, wherein the surfactant is at least one of a silicone surfactant and a fluorosurfactant.
<9> The content of the surfactant in the active energy ray curable resin composition is 0.0001% by mass to 5.0% by mass with respect to the nonvolatile content of the active energy ray curable resin composition It is a laminated body in any one of said <7> to <8>.
<10> An article having the laminate according to any one of <1> to <9> on its surface.
<11> The article according to <10>, which is a mirror.
<12> The article according to <11>, which is at least one of a bathroom and a washbasin.
<13> The wire mesh of 1 cm apart stands at a position 1 m away from the mirror surface in the normal direction, and when the image of the wire mesh is visually evaluated, the image of the wire mesh does not have distortion. It is an article according to any of 11> to <12>.
<14> An active energy ray-curable resin composition used for forming the primer layer of the laminate according to any one of <1> to <6>,
It is an active energy ray curable resin composition characterized by containing a surfactant.
<15> The active energy ray curable resin composition according to <14>, wherein the surfactant is at least one of a silicone surfactant and a fluorine surfactant.
The content of <16> said surfactant is 0.0001 mass%-5.0 mass% with respect to the non volatile matter of the said active energy ray curable resin composition of said <14> to <15> It is an active energy ray curable resin composition as described in any one.
<17> The method for producing a laminate according to any one of <1> to <6>,
A method of producing a laminate comprising a primer layer forming step of applying an active energy ray curable resin composition containing a surfactant onto the substrate and curing it to form the primer layer. It is.
<18> The method of producing a laminate according to <17>, wherein the surfactant is at least one of a silicone surfactant and a fluorine surfactant.
<19> The content of the surfactant in the active energy ray curable resin composition is 0.0001% by mass to 5.0% by mass with respect to the nonvolatile content of the active energy ray curable resin composition It is a manufacturing method of the laminated body in any one of said <17> to <18>.

  According to the present invention, the above-mentioned various problems in the prior art can be solved, and the above object can be achieved, and a laminate having at least one of antifogging property and antifouling property and provided with a primer layer is an end. A laminate having excellent visibility of parts, a method for producing the same, an article using the laminate, and an active energy ray curable resin composition applicable to the formation of the primer layer of the laminate Can.

FIG. 1: is a schematic diagram of an example of the cross-sectional profile of a laminated body. FIG. 2 is a schematic cross-sectional view of an example of the laminate of the present invention. FIG. 3 is a schematic cross-sectional view of an example of the article of the present invention. FIG. 4A is a schematic view for explaining the method of the cloudiness test with steam. FIG. 4B is a schematic view for explaining the method of the cloudiness test with steam.

(Laminate)
The laminate of the present invention has at least a substrate, a primer layer, and a functional layer, and further has other members as required.

When a functional layer having anti-fogging and anti-soiling properties is formed on the surface of a substrate by a coating method, the image is distorted at the end and the visibility is reduced. The decrease in visibility becomes more remarkable as the average thickness of the functional layer is larger (for example, when the average thickness is 10 μm or more).
The present inventors diligently studied to solve the problems. And the present inventors confirmed that the cause to which visibility fell was the convex part formed in the edge part. Furthermore, when the present inventors formed the said functional layer by the apply | coating method, the coating material apply | coated to the edge part of the said base material raised with surface tension, and confirmed that a convex part was formed in the edge part .
Then, the inventors of the present invention have found that the formation of the convex portion at the end can be suppressed by containing the surfactant in the composition for forming the primer layer by repeating intensive studies. It came to completion.

<Features of laminate>
The laminate has the following features.
It has the said primer layer and the said functional layer.
The surface on the functional layer side of the end portion of the laminate has a convex portion having a top side portion along the end side of the end portion.
The height of the protrusion is 10 μm or less, the width of the protrusion is 15 mm or less, and the edge and the top side in a cross section orthogonal to the direction of the edge and the surface direction of the surface The length between and is 5.0 mm or less.
Here, the "end" means an area including an edge and its vicinity including the edge.

Here, each length in the cross section can be determined, for example, by measuring a cross-sectional profile of the laminate.
Here, a schematic view of an example of the cross-sectional profile is shown in FIG.
FIG. 1 is a schematic view of an example of a cross-sectional profile.
FIG. 1 is a schematic view of a profile of a cross section orthogonal to the direction of the edge in the laminate and the surface direction of the surface on the functional layer side. The solid line (f) having a convex portion represents the surface of the functional layer. The symbol (t) indicates the top (peak side) of a mountain, the symbol (a) indicates an edge, the symbol (h) indicates the height of a ridge, the symbol (w) indicates the width of a peak, and the symbol (L) indicates the horizontal distance (length between the end and the top) between the end (a) and the top of the mountain (t).
The height (h) of the mountain is the distance from the top side (t) to the extension line (i) of the horizontal surface (f1) on the surface on the functional layer side.
The width (w) of the convex portion is the distance from the bottom point (f2) on the central portion side of the surface in the convex portion to the line (ii) orthogonal to the end side (a) and the surface on the functional layer side .
The horizontal distance (l) is the distance between the line (ii) and the perpendicular (iii) drawn from the top (t) to the extension (i).

In the present invention, the convex portion at the end is not necessarily only that the height is small. In addition, the width of the projections needs to be short. That is, in the case of a convex portion having a large width even if the height is low, in other words, a gently wide convex portion, the visibility is poor. Further, the position of the apex of the convex portion is also important, and if it is too far from the end side, the visibility is poor even if the height is small and narrow.
Therefore, all of the following (1) to (3) are required as the condition for improving the visibility.
(1) The height of the convex portion [height of mountain (h)] is 10 μm or less.
(2) The width (w) of the projection is 15 mm or less.
(3) The length between the end side and the top side [horizontal distance (l)] is 5.0 mm or less.
When the height of the convex portion exceeds 10 μm, distortion of the image is strongly recognized by refraction. Therefore, even if the width of the projection and the length between the end side and the top side satisfy the above (2) and (3), the height of the projection does not satisfy the above (1). , Deterioration of visibility can not be suppressed.
The length between the end side and the top side is correlated with the width of the distortion of the image to be recognized (= the length from the end side to the center until the distortion of the image disappears). When the height of the convex portion satisfies the above (1), the degree of refraction is not so strong and the distortion of the image is not so strong. However, if the length between the end side and the top side exceeds 5.0 mm, it will be recognized as a distorted area.
When the width of the convex portion exceeds 15 mm, the width of the distortion of the image to be recognized (= the length from the end side to the center direction until the distortion of the image disappears) becomes large. Therefore, even if the height of the projection and the length between the end side and the top side satisfy the above (1) and (3), the width of the projection does not satisfy the above (2). The degree of refraction is not so strong and the distortion of the image is not so strong and it is perceived as a distorted area.

<< Height of convex part >>
The height of the convex portion is 10 μm or less, preferably 8.0 μm or less, more preferably 7.0 μm or less, and particularly preferably 5.5 mm or less. There is no restriction | limiting in particular in the lower limit of the height of the said convex part, According to the objective, it can select suitably, For example, the height of the said convex part may be 1.0 micrometer or more, or 2. It may be 0 μm or more, or 4.0 μm or more.

<< width of convex part >>
The width of the convex portion is 15 mm or less, preferably 14 mm or less, more preferably 10 mm or less, and particularly preferably 6.0 mm or less. There is no restriction | limiting in particular as a lower limit of the width | variety of the said convex part, According to the objective, it can select suitably, For example, the width of the said convex part may be 1.0 mm or more, and 3.0 mm It may be above or 5.0 mm or more.

<< Length between edge and top >>
The length (length between the end side and the top side) is 5.0 mm or less, preferably 4.5 mm or less, more preferably 3.5 mm or less, and particularly preferably 3.0 mm or less. There is no restriction | limiting in particular as a lower limit of the said length, According to the objective, it can select suitably, For example, 0.5 mm or more may be sufficient as the said length, and it is 1.0 mm or more. It may be 2.0 mm or more.

  That is, as a condition excellent in the visibility of the end, the height of the convex is particularly preferably 5.5 mm or less, the width of the convex is particularly preferably 6.0 mm or less, and the length (edge side 3.0 mm or less is especially preferable as for the length between and a top side.

The cross-sectional profile of the laminate can be measured, for example, by the following method.
Using a KLA-Tencor Stylus Surface Profilometer P-15, the cross-sectional profile of the surface at the end is measured under the following measurement conditions.
〔Measurement condition〕
・ X scan size = 10 to 100 mm
・ Scan Speed = 200μm / sec
・ Sampling Rate = 200Hz
・ Multi-Scan Average = 1
Applied Force = 2.00 mg
Stylus Radius = 2.00 μm

<Base material>
There is no restriction | limiting in particular as said base material, According to the objective, it can select suitably, For example, resin-made base materials, inorganic-made base materials, etc. are mentioned.

<< Inorganic base material >>
Examples of the inorganic base include a glass base, a quartz base, and a sapphire base.

There is no restriction | limiting in particular as said glass-made base materials, According to the objective, it can select suitably, For example, silicate glass (silicate glass), soda lime glass, potash glass etc. are mentioned.
The glass substrate may be tempered glass, laminated glass, heat-resistant glass, or the like.
The glass substrate may be used in any application such as window glass for automobiles, window glass for buildings, lenses, mirrors, goggles and the like.
The shape of the glass substrate is generally plate-like, but may be any shape such as sheet-like or curved.

<< Resin base material >>
There is no restriction | limiting in particular as a material of the said resin-made base materials, According to the objective, it can select suitably, For example, triacetyl cellulose (TAC), polyester (TPEE), polyethylene terephthalate (PET), polyethylene naphthalate ( PEN), polyimide (PI), polyamide (PA), aramid, polyethylene (PE), polyacrylate, polyether sulfone, polysulfone, polypropylene (PP), polystyrene, diacetyl cellulose, 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 (CO ), PC / PMMA laminate, such as rubber additives PMMA and the like.

  The substrate preferably has transparency.

There is no restriction | limiting in particular as a shape of the said base material, Although it can select suitably according to the objective, It is preferable that it is a film form.
When the substrate is in the form of a film, the average thickness of the substrate is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 5 μm to 1,000 μm, and more preferably 50 μm to 500 μm.

  Characters, patterns, images and the like may be printed on the surface of the substrate.

  The character, the pattern, and the image may be formed on the surface of the base material in order to increase the adhesion between the base material and the molding material when molding the laminate, or from the flow pressure of the molding material when molding. A binder layer may be provided to protect the As a material of the said binder layer, various adhesives other than various binders, such as an acryl type, a urethane type, polyester type, polyamide type, ethylene butyl alcohol type, ethylene vinyl acetate copolymer type, can be used. The binder layer may be provided in two or more layers. The binder to be used can select the thing with the thermosensitivity suitable for a molding material, and a pressure sensitivity.

The surface of the base opposite to the functional layer may have a wrinkled pattern. By doing so, blocking at the time of stacking a plurality of the laminates is prevented, the handleability in the later step is improved, and the article can be manufactured efficiently.
The wrinkle pattern can be formed, for example, by embossing.
Here, blocking means that when a plurality of sheets are stacked, it becomes difficult to separate the sheets.

<Primer layer>
The functional layer may not have sufficient adhesion to the substrate. So, in the said laminated body, the primer layer which improves the adhesiveness of the said functional layer to the said base material is distribute | arranged between the said base material and the said functional layer.

When the primer layer is thin, the adhesion improving effect is insufficient. Therefore, the average thickness of the primer layer is preferably 0.5 μm or more in that respect.
Furthermore, as average thickness of the said primer layer, 0.5 micrometer-20 micrometers are more preferable, 0.5 micrometer-10 micrometers are still more preferable, 0.5 micrometer-5 micrometers are especially preferable.
When the average thickness of the primer layer is in a more preferable range, it is exposed to high temperature steam (eg, 60 ° C. or more), thermal shock (eg, rapid change from -20 ° C. to 80 ° C.), alkaline detergent Also, the adhesion is unlikely to be lowered, and the peeling of the functional layer can be prevented.

The average thickness is determined by the following method.
The thickness of the primer layer can be measured by observing the cross section of the laminate with a field emission scanning electron microscope S-4700 (trade name; manufactured by Hitachi High-Technologies Corporation). Measure at any 10 points, and let the average value be the average thickness. In addition, in this case, it measures in the location except the edge part of the said laminated body.

  The primer layer can be formed, for example, by applying an active energy ray-curable resin composition. That is, the primer layer is, for example, a cured product obtained by curing an active energy ray curable resin composition by active energy rays.

<< Active energy ray curable resin composition >>
The active energy ray-curable resin composition contains, for example, a surfactant and, if necessary, further contains other components such as urethane (meth) acrylate, a photopolymerization initiator, and a solvent.
When the active energy ray-curable resin composition contains the surfactant, the height of the convex portion at the end of the primer layer obtained, the width of the convex portion, and the distance between the end side and the top side Can be kept short. As a result, the height of the convex portion at the end of the functional layer formed on the primer layer, the width of the convex portion, and the length between the end side and the top side can also be reduced.

<<< surfactant >>>
Examples of the surfactant include silicone surfactants, acrylic surfactants, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, fluorine surfactants, and the like. Can be mentioned. Among these, silicone surfactants are preferable because they can significantly reduce the surface tension.

  As said silicone type surfactant, modified silicones, such as polyester modified silicone and polyether modified silicone, can be used, for example. Among these, polyether-modified silicones are preferred in that the surface tension can be significantly reduced.

As the polyether-modified silicone, polyether-modified polydimethylsiloxane is preferably used.
As the polyester modified silicone, polyester modified polydimethylsiloxane is preferably used.

  As a commercial item of the silicone type surfactant, for example, BYK-347, BYK-348, BYK-UV 3500, BYK-UV 3510, BYK-UV 3530, BYK-UV 3570 (trade names of BYK Corporation), KP 323 (Shin-Etsu Co., Ltd.) Chemical Industry Co., Ltd. trade name) etc. are mentioned. Among these, BYK-UV 3500, BYK-UV 3510, and KP 323 are preferable because the wettability and spreadability of the composition (coating material) for forming the functional layer is further improved.

Examples of the fluorine-based surfactant include those having a structure having a perfluoroalkyl group.
As a commercial item of the said fluorochemical surfactant, Megafac F-470, F-471, F-472SF, F-474, F-475, R-30, F-477, F-478, F-. 479, BL-20, R-61, R-90 (above, DIC Corporation product name), FC-170C, FC-4430, FC-4432 (above, Sumitomo 3M Corporation product name), etc. may be mentioned .

  The surfactant may or may not have a (meth) acryloyl group.

  There is no restriction | limiting in particular as content of the said surfactant in the said active energy ray curable resin composition, Although it can select suitably according to the objective, For the non volatile matter of the said active energy ray curable resin composition On the other hand, 0.0001 mass% to 5.0 mass% is preferable, 0.0001 mass% to 3.0 mass% is more preferable, and 0.005 mass% to 1.0 mass% is particularly preferable. Within the above-mentioned particularly preferable range, the adhesiveness and the reduction of the surface tension can be highly compatible.

<<< Urethane (Meth) Acrylate>>>
There is no restriction | limiting in particular as said urethane (meth) acrylate, According to the objective, it can select suitably, For example, aliphatic urethane (meth) acrylate, aromatic urethane (meth) acrylate, etc. are mentioned. Among these, aliphatic urethane (meth) acrylates are preferable.

  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, Non-volatile of the said active energy ray curable resin composition 40 mass%-80 mass% are preferable with respect to a part, 50 mass%-75 mass% are more preferable, 60 mass%-70 mass% are especially preferable.

<<< photoinitiator >>>
As a specific example of the said photoinitiator, the specific example of the photoinitiator illustrated in description of the said functional layer mentioned later is mentioned, for example.

<<<solvent>>>
As a specific example of the said solvent, the specific example of the solvent illustrated in description of the said functional layer mentioned later is mentioned, for example.

  The active energy ray curable resin composition preferably further contains a (meth) acrylate having an alkylene oxide structure. Examples of the (meth) acrylate having an alkylene oxide structure include glycerin alkoxy tri (meth) acrylate, pentaerythritol alkoxy tetra (meth) acrylate, isocyanuric acid alkoxy tri (meth) acrylate, bisphenol A alkoxy di (meth) acrylate, Examples thereof include polyalkylene glycol di (meth) acrylate, trimethylolpropane alkoxy tri (meth) acrylate and the like. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

  There is no restriction | limiting in particular as content of the (meth) acrylate which has the said alkylene oxide structure in the said active energy ray curable resin composition, Although it can select suitably according to the objective, The said active energy ray curable resin 15 mass%-50 mass% are preferable with respect to the non volatile matter of a composition, 20 mass%-45 mass% are more preferable, and 25 mass%-38 mass% are especially preferable.

  The application method 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, die coating, spray coating, roll coating, gravure coating , Microgravure coating, lip coating, air knife coating, curtain coating, comma coating method, dipping method and the like.

  The active energy ray curable resin composition is cured by irradiation 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) Wires, etc.), microwaves, high frequencies, etc.

<Functional layer>
The functional layer has at least one of antifogging property and antifouling property.

<< pure water contact angle >>
The pure water contact angle on the surface of the functional layer is preferably 80 ° or more, more preferably 90 ° or more, and particularly preferably 100 ° or more. There is no restriction | limiting in particular as an upper limit of the said pure water contact angle, According to the objective, it can select suitably, The said pure water contact angle mentions 130 degrees or less, 150 degrees or less, 170 degrees or less etc., for example Be

The pure water contact angle is measured using the contact angle meter PCA-1 (manufactured by Kyowa Interface Chemical Co., Ltd.) under the following conditions. Distilled water is put into a plastic syringe, and a stainless steel needle is attached to the tip of the syringe and dropped onto the evaluation surface (functional layer surface).
Water dripping amount: 2 μL
Measurement temperature: 25 ° C
Water is dropped, and the contact angle after 5 seconds has elapsed is measured at any ten places on the surface of the functional layer, and the average value is taken as the pure water contact angle.

<< hexadecane contact angle >>
35 degrees or more are preferable, as for the hexadecane contact angle of the surface of the said functional layer, 40 degrees or more are more preferable, and 60 degrees or more are especially preferable. 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, The said pure water contact angle is 100 degrees or less, 120 degrees or less, 150 degrees or less etc., for example .

The said hexadecane contact angle is measured on condition of the following using PCA-1 (made by Kyowa Interface Chemical Co., Ltd.) which is a contact angle meter. Put hexadecane in a plastic syringe, attach a Teflon-coated stainless steel needle to its tip, and drop it on the evaluation surface (functional layer surface).
Drop amount of hexadecane: 1 μL
Measurement temperature: 25 ° C
The contact angle after 20 seconds of dropping hexadecane is measured at any 10 points on the surface of the functional layer, and the average value is taken as the hexadecane contact angle.

  When the pure water contact angle is in the above preferable range and the hexadecane contact angle is in the above preferable range, aqueous stains and / or oily stains such as magic ink, fingerprints, sweat, cosmetics (such as foundation and UV protector) are Even in the case of adhesion, these stains are prevented from penetrating into the lower layer of the bulk, and in addition to the antifogging property, the antifouling property is also excellent.

<< Coefficient of dynamic friction >>
There is no restriction | limiting in particular as a dynamic friction coefficient of the said functional layer, Although it can select suitably according to the objective, 0.40 or less is preferable, 0.37 or less is more preferable, and 0.30 or less is especially preferable. When the dynamic friction coefficient is 0.40 or less, the slipperiness of the wiping material is good and it is easy to wipe off even if dirt adheres. In addition, the effect of releasing the force is generated, and the functional layer is not easily damaged.
There is no restriction | limiting in particular as a lower limit of the dynamic friction coefficient of the said functional layer, Although it can select suitably according to the objective, For example, 0.10 or more is preferable for the dynamic friction coefficient of the said functional layer.

The dynamic friction coefficient is determined by the following method.
The dynamic friction coefficient is measured using Triboster TS501 (trade name; manufactured by Kyowa Interface Science Co., Ltd.). Attach a BEMCOT (registered trademark) M-3 II (trade name; manufactured by Asahi Kasei Corporation) to the surface contactor with a double-sided tape, measure load 50 g / cm ² , measure speed 1.7 mm / s, measure distance 20 mm, Measure at 12 locations and use the average value as the dynamic friction coefficient.

<< Average thickness >>
In order to suppress fogging for a predetermined time or more (for example, 10 minutes or more) in an atmosphere of high temperature and high humidity (for example, 35 ° C. and 85% RH), it is effective to make the thickness of the functional layer be a certain thickness or more.
From that viewpoint, the average thickness of the functional layer is preferably 10 μm or more, more preferably 20 μm or more, and particularly preferably 30 μm or more.
If the average thickness of the functional layer is large, the height of the convex portion at the end is also increased accordingly. Therefore, the average thickness is preferably less than 45 μm, and more preferably 40 μm or less.

The average thickness is determined by the following method.
The thickness of the functional layer can be measured by observing the cross section of the laminate with a field emission scanning electron microscope S-4700 (trade name; manufactured by Hitachi High-Technologies Corporation). Measure at any 10 points, and let the average value be the average thickness. In addition, in this case, it measures in the location except the edge part of the said laminated body.

<< Active energy ray curable resin composition >>
The functional layer is, for example, a cured product of an active energy ray-curable resin composition.
The active energy ray-curable resin composition preferably contains a water repellent monomer having a water repellent molecular structure, a surfactant, and further contains other monomers, a polymerization initiator, a solvent, and the like as required.

<<< Water-repellent monomer >>>
The water repellent monomer has a water repellent molecular structure. The water repellent molecular structure in the present invention includes a structure having fluorine or silicon, and examples thereof include a fluoroalkyl structure, a perfluoropolyether structure, a dimethylsiloxane structure and the like.

As the water-repellent monomer containing a perfluoropolyether group (meth) acrylate are preferable, as the perfluoropolyether _{group, - (O-CF 2 CF} 2) -, - (O-CF 2 CF 2 CF 2 ) -, or _{- (O-CF 2 C (} CF 3) F) - a compound containing a repeating structure is preferred. Examples of 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 Sartmar, KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd. .

  When the water repellent monomer has a perfluoropolyether group (perfluoropolyether structure), not only the surface energy of the functional layer can be lowered but also the molecular chain is flexible and easy to move, so that dirt can be easily wiped off. In addition, the dynamic friction coefficient of the functional layer can be lowered to enhance scratch resistance. In that respect, the water repellent monomer preferably has a perfluoropolyether group (perfluoropolyether structure).

  The water repellent monomer is, for example, (meth) acrylate. That is, the water repellent monomer is, for example, a (meth) acrylate having a water repellent molecular structure.

  There is no restriction | limiting in particular as content of the said water-repellent monomer in the said active energy ray curable resin composition, Although it can select suitably according to the objective, The monomer whole quantity in the said active energy ray curable resin composition 0.001 mass%-10 mass% are preferable, 0.001 mass%-5.0 mass% are more preferable, 0.01 mass%-5.0 mass% are especially preferable.

<<< surfactant >>>
There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, the detail and the preferable aspect are components of the said active energy ray curable resin composition in description of the said primer layer. The details of the surfactant as and the same as the preferred embodiment.

  The active energy ray curable resin composition for forming the primer layer contains the surfactant, and the active energy ray curable resin composition for forming the functional layer comprises the surfactant. By containing, the height of the convex part at the end of the functional layer formed on the primer layer, the width of the convex part, and the length between the end side and the top side can be further reduced. it can.

  There is no restriction | limiting in particular as content of the said surfactant in the said active energy ray curable resin composition, Although it can select suitably according to the objective, For the non volatile matter of the said active energy ray curable resin composition On the other hand, 0.0001 mass% to 5.0 mass% is preferable, 0.0001 mass% to 3.0 mass% is more preferable, and 0.005 mass% to 1.0 mass% is particularly preferable.

<<< Other monomer >>>
As said other monomer, a hydrophilic monomer, a crosslinking agent, etc. are mentioned, for example.

-Hydrophilic monomer-
The hydrophilic monomer has, for example, an alkylene oxide equivalent of less than 100 and an acrylic equivalent of 200 to 500.

Here, the alkylene oxide equivalent is the mass of monomer per mol of alkylene oxide group, and is obtained by dividing the molecular weight of the monomer by the number of alkylene oxide per molecule of the monomer.
The acrylic equivalent is the monomer mass per 1 mol of (meth) acrylic group, and is obtained by dividing the molecular weight of the monomer by the number of (meth) acrylic groups [also referred to as (meth) acryloyl groups] per 1 molecule of the monomer. Be

As a carbon number of the alkylene group in the said alkylene oxide, 1-12 are preferable and 1-4 are more preferable.
Examples of the alkylene oxide include methylene oxide (carbon number 1), 1,2-ethylene oxide (carbon number 2), 1,3-propylene oxide (carbon number 3), and 1,2-propylene oxide (carbon number 3). And 1,4-butylene oxide (carbon number 4).

  There is no restriction | limiting in particular as a lower limit of the said alkylene oxide equivalent in the said hydrophilic monomer, According to the objective, it can select suitably, As said alkylene oxide equivalent, 30 or more, 40 or more etc. are mentioned, for example.

The hydrophilic monomer has a (meth) acryloyl group. There is no restriction | limiting in particular as a number of the said (meth) acryloyl group in the said hydrophilic monomer, Although it can select suitably according to the objective, 2-6 are preferable and 2-4 are more preferable.
The (meth) acryloyl group means an acryloyl group or a methacryloyl group.

  The hydrophilic monomer is not particularly limited as long as, for example, the alkylene oxide equivalent is less than 100 and the acrylic equivalent is 200 to 500, and can be appropriately selected according to the purpose. For example, alkoxylated trimethylol Propane tri (meth) acrylate, alkoxylated glycerin tri (meth) acrylate, alkoxylated pentaerythritol tetra (meth) acrylate, polyalkylene glycol di (meth) acrylate and the like can be mentioned. Examples of the alkoxylated trimethylolpropane tri (meth) acrylate include ethoxylated trimethylolpropane tri (meth) acrylate.

  There is no restriction | limiting in particular as molecular weight of the said hydrophilic monomer, Although it can select suitably according to the objective, 300-2,500 are preferable, 400-2,000 are more preferable, 600-1,500 are especially preferable. preferable.

  There is no restriction | limiting in particular as content of the said hydrophilic monomer in the said active energy ray curable resin composition, Although it can select suitably according to the objective, For the non volatile matter of the said active energy ray curable resin composition On the other hand, 55 mass%-90 mass% are preferable, and 60 mass%-75 mass% are more preferable. When the content is within the preferable range, the functional layer is less likely to be cloudy, scratched, and less likely to be applied to medicine.

-Crosslinking agent-
The crosslinking agent is different from the hydrophilic monomer, and for example, has an alkylene oxide equivalent of 100 or more. Furthermore, the crosslinking agent has, for example, an acrylic equivalent of less than 400.
In the present invention, a crosslinking agent not having an alkylene oxide is also included in the crosslinking agent.
The crosslinking agent is, for example, non-alicyclic. That is, the crosslinking agent does not have an alicyclic structure. An alicyclic structure is a ring structure consisting of three or more carbons.

  Examples of the alkylene oxide include ethylene oxide and 1,2-propylene oxide.

  There is no restriction | limiting in particular as a lower limit of the said acryl equivalent in the said crosslinking agent, According to the objective, it can select suitably, For example, 100 or more etc. are mentioned as said acryl equivalent.

  The crosslinking agent has a (meth) acryloyl group. There is no restriction | limiting in particular as a number of the said (meth) acryloyl group in the said crosslinking agent, Although it can select suitably according to the objective, 2-6 are preferable.

  The crosslinking agent is not particularly limited as long as the alkylene oxide equivalent is 100 or more and the acrylic equivalent is less than 400, and can be appropriately selected according to the purpose. For example, pentaerythritol alkoxy tetra (meth) acrylate And aliphatic urethane (urethane) acrylate and ethoxylated bisphenol A diacrylate.

  There is no restriction | limiting in particular as a molecular weight of the said crosslinking agent, Although it can select suitably according to the objective, 300-2,500 are preferable, 400-2,000 are more preferable, 500-1,900 are especially preferable. .

  There is no restriction | limiting in particular as content of the said crosslinking agent in the said active energy ray curable resin composition, Although it can select suitably according to the objective, With respect to the non volatile matter of the said active energy ray curable resin composition 5 to 40 mass% is preferable, 20 to 35 mass% is more preferable, and 20 to 30 mass% is particularly preferable. When the content is less than 5% by mass, scratch resistance and chemical resistance may be reduced. If the content exceeds 40% by mass, the antifogging properties may be reduced.

  Here, examples of the hydrophilic monomer and the crosslinking agent, and their alkylene oxide equivalents and acrylic equivalents are listed below.

In Table 1, "AO" represents an alkylene oxide.
The details of the monomers listed in Table 1 are as follows.
[Hydrophilic monomer]
SR9035: manufactured by Sartomer, ethoxylated (15) trimethylolpropane triacrylate (15) represents that the average number of ethylene oxide groups contained in 1 mole is 15.
-ATM-35E: manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated pentaerythritol tetraacrylate-A-GLY-20E: manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated glycerin triacrylate-A-600: Shin-Nakamura Chemical Co., Ltd. Made, polyethylene glycol diacrylate A-GLY-9E: manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated glycerin triacrylate A-400: manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene glycol diacrylate [crosslinking agent]
-EBECRYL 40: manufactured by Daicel Ornex Co., Ltd., pentaerythritol alkoxy tetraacrylate-PU 610: manufactured by Miwon, aliphatic urethane acrylate (acrylic group number 6, molecular weight: 1,800)
ABE-300: Shin-Nakamura Chemical Co., Ltd., ethoxylated bisphenol A diacrylate

<<< photoinitiator >>>
Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photoacid generator, a bisazide compound, hexamethoxymethylmelamine, tetramethoxyglycolyl and the like.
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 Mixture of esters 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide

It is preferable that the said photoinitiator does not contain a nitrogen atom in a constitutent element from the point which prevents the yellowing in an external appearance.
On the other hand, from the viewpoint of preventing yellowing in appearance, the photopolymerization initiator may have only C, H and O as constituent elements, or C, H, P and O as constituent elements. 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 matter of the said active energy ray curable resin composition 0.1 mass%-10 mass% are preferable, 0.1 mass%-5 mass% are more preferable, 1 mass%-5 mass% are especially preferable.

<<<solvent>>>
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, the 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, dimethylsulfoxide, dimethylacetamide and the like.

As the solvent, a solvent having a boiling point of 80 ° C. or more is preferable from the viewpoint of obtaining a functional 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, and 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 include methyl carbitol, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate and the like.

  There is no restriction | limiting in particular as content of the said solvent in the said active energy ray curable resin composition, According to the objective, it can select suitably.

  The active energy ray curable resin composition is cured by irradiation 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) Wires, etc.), microwaves, high frequencies, etc.

Here, an example of the said laminated body is demonstrated.
FIG. 2 is a schematic cross-sectional view of an example of the laminate of the present invention.
The laminate of FIG. 2 has a base 11, a primer layer 12 and a functional layer 13.

(Active energy ray curable resin composition)
The active energy ray-curable resin composition of the present invention contains a surfactant and, if necessary, further contains other components such as urethane (meth) acrylate, a photopolymerization initiator and a solvent.
The active energy ray curable resin composition is used to form the primer layer of the laminate of the present invention.

  The details and preferred embodiments of the components of the active energy ray curable resin composition are the same as the details and preferred embodiments of the components of the active energy ray curable resin composition in the description of the primer layer of the laminate. .

(Method of manufacturing laminate)
The method for producing a laminate of the present invention at least includes a primer layer forming step, preferably includes a functional layer forming step, and further includes other steps as necessary.

  The method of producing the laminate is a preferred method of producing the laminate of the present invention.

<Primer layer formation process>
As said primer layer formation process, the process of apply | coating and hardening the active energy ray curable resin composition for primer layer formation on the said base material, and forming the said primer layer etc. are mentioned.
Details of the components of the active energy curable resin composition for forming the primer layer, and preferred embodiments are the details of the components of the active energy ray curable resin composition in the description of the primer layer of the laminate, and preferred embodiments and It is the same.

<Functional layer formation process>
In the functional layer forming step, for example, ultraviolet light is generated in an atmosphere having an oxygen concentration of less than 1% by volume with respect to an uncured layer formed of the active energy ray curable resin composition for functional layer formation on the primer layer. The process of irradiating and forming the said functional layer etc. are mentioned.
The details of the components of the active energy ray curable resin composition for forming the functional layer and the preferred embodiments are the details of the components of the active energy ray curable resin composition in the description of the functional layer of the laminate and the preferred embodiments Is the same as

When forming the functional layer, by performing ultraviolet irradiation in an atmosphere having an oxygen concentration of less than 1 vol%, as a result of excellent curability, a functional layer having a low dynamic friction coefficient and a high contact angle can be obtained.
Examples of the atmosphere having an oxygen concentration of less than 1% by volume include an inert gas atmosphere such as a nitrogen atmosphere.

(Articles)
The article of the present invention has the above-mentioned laminate of the present invention on the surface, and further has other members as required.
There is no restriction | limiting in particular as said articles | goods, According to the objective, it can select suitably, For example, window materials, such as a glass window, a refrigeration / freezer showcase, a window of a car, a mirror in a bathroom, a car side mirror etc. Mirrors, bathroom floors and walls, solar panels, security cameras and the like. The mirror is preferably a mirror, and more preferably a mirror for a bathroom or a washbasin.

Here, an example of a mirror which is an article of the present invention will be described with reference to FIG.
The article of FIG. 3 has a substrate 11, a primer layer 12, and a functional layer 13 in this order. Furthermore, the metal layer 14 and the back surface protective layer 15 are provided in this order on the side opposite to the primer layer 12 side of the substrate 11.
The base material 11 is, for example, soda lime silicate glass manufactured by the float method or the like, and the metal layer 14 is formed on the back surface thereof by silver mirror reaction, catalytic accelerator accelerator method, sensitizer activator method, vacuum evaporation method or the like. Be done. The combination of the substrate 11 and the metal layer 14 is not limited to this, and, for example, a glass mirror on which a multilayer film of a dielectric is formed by a vacuum evaporation method or a sol-gel method, or a plastic mirror such as polycarbonate or polyethylene terephthalate It may be a metal mirror made of stainless steel, bronze or the like.
The back surface protective layer 15 is provided adjacent to the metal layer 14 for the purpose of preventing the corrosion and deterioration of the metal layer 14. The back surface protective layer 15 may be a single layer or a multilayer. There is no restriction | limiting in particular as a material of the back surface protective layer 15, According to the objective, it can select suitably, For example, metal (for example, copper etc.), resin (for example, epoxy resin, unsaturated polyester resin, a fluorine resin, Acrylic resin, urethane resin, melamine resin, silicone resin, etc. may be mentioned.

  If the article is a mirror, stand with a 1 cm wire mesh at a position 1 m away from the mirror surface in the normal direction, and when the image of the reflected wire mesh is visually evaluated, the image of the wire mesh is distorted It is preferred not to occur.

  The laminate may be formed on a part of the surface of the article or may be formed on the entire surface.

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

<Average thickness>
The thickness of the functional layer and the primer layer was measured by observing the cross section of the laminate with a field emission scanning electron microscope S-4700 (trade name; manufactured by Hitachi High-Technologies Corporation). It measured at five arbitrary places other than an edge part, and made the average value the average thickness.

<Cross-sectional profile of surface at end>
Using a KLA-Tencor Stylus Surface Profilometer P-15, the cross-sectional profile of the surface at the end was measured under the following measurement conditions.
〔Measurement condition〕
・ X scan size = 10 to 100 mm
・ Scan Speed = 200μm / sec
・ Sampling Rate = 200Hz
・ Multi-Scan Average = 1
Applied Force = 2.00 mg
Stylus Radius = 2.00 μm

<Visibility>
A wire mesh with an aperture of 1 cm was stood at a position 50 cm or 1 m away from the mirror surface in the normal direction, and the image of the reflected wire mesh was visually evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
:: Standing with a 1 cm mesh at a distance of 50 cm from the mirror surface in the direction of its normal, when the image of the reflected mesh was visually evaluated, the distortion of the image at the end of the mirror is not bothersome The
:: Standing with a 1 cm mesh at a distance of 50 cm from the mirror surface in the direction of its normal, the image of the reflected mesh was visually evaluated, but distortion of the image was observed at the end of the mirror When I stood with a 1-cm wire mesh at a distance of 1 m and evaluated the image of the reflected wire mesh visually, the distortion of the image at the end of the mirror was not noticeable.
X: Standing with a wire mesh of 1 cm apart at a position 1 m away from the mirror surface in the normal direction, the image of the reflected wire mesh was visually evaluated and found that the image was distorted at the end of the mirror and bothersome.

<Pure water contact angle>
The pure water contact angle was measured using the contact angle meter PCA-1 (manufactured by Kyowa Interface Chemicals Co., Ltd.) under the following conditions. Distilled water was put into a plastic syringe, and a stainless steel needle was attached to the tip and dropped onto the evaluation surface (functional layer surface).
Water dripping amount: 2 μL
Measurement temperature: 25 ° C
Water was dropped and the contact angle after 5 seconds was measured at any ten places on the surface of the functional layer, and the average value was taken as the pure water contact angle.

<Hexadecane contact angle>
The hexadecane contact angle was measured using the contact angle meter PCA-1 (manufactured by Kyowa Interface Chemicals Co., Ltd.) under the following conditions. Hexadecane was placed in a plastic syringe, and a Teflon-coated stainless steel needle was attached to the tip of the syringe, and dropped onto the evaluation surface (functional layer surface).
Drop amount of hexadecane: 1 μL
Measurement temperature: 25 ° C
The contact angle after 20 seconds of dropping of hexadecane was measured at any 10 points on the surface of the functional layer, and the average value was taken as the hexadecane contact angle.

<Dynamic friction coefficient>
It measured using Triboster TS501 (brand name; Kyowa Interface Science Co., Ltd. make). Attach a BEMCOT (registered trademark) M-3 II (trade name; manufactured by Asahi Kasei Corporation) to the surface contactor with a double-sided tape, measure load 50 g / cm ² , measure speed 1.7 mm / s, measure distance 20 mm, It measured at 12 places and made the average value the dynamic friction coefficient.

<Anti-fog property>
The test piece was exposed to 35 ° C. and 85% RH after being left in a normal temperature environment for 2 hours. The surface was visually observed and the antifogging property was evaluated by the following evaluation criteria.
〔Evaluation criteria〕
:: Less than 30% of the area with low visibility due to cloudiness or water droplets even after 15 minutes.
○: Less than 30% of the area with poor visibility due to cloudiness or water droplets until 10 minutes later.
Δ: Less than 30% of the area with poor visibility due to cloudiness or water droplets until 5 minutes later.
X: The area of low visibility due to cloudiness or water droplets in 5 minutes is greater than 30%.

<Anti-fog property after heating>
About half of the container was filled with water. The introduced water was heated by a heater to keep it at 55 ° C, and the atmospheric temperature of the upper space in the vessel was kept at 35 ° C. The laminate (sample) was placed in the container so as not to be in contact with water (hot water) (FIG. 4A). Then, about 40 ° C. hot water was applied to the functional layer of the laminate (sample) (FIG. 4B). Then, it returned to the state of FIG. 4A, and after 10 minutes, the appearance of cloudy was visually observed. It evaluated by the following evaluation criteria.
〔Evaluation criteria〕
:: There was no change in appearance on the surface of the functional layer.
○: A change in appearance such as white haze and water film formation was observed on part of the surface of the functional layer.
X: The surface of the functional layer was entirely changed in appearance such as white haze and water film formation.

<Antifouling property>
The surface of the functional layer was stained with Sharpie PROFESSIONAL (black oily magic, trade name, manufactured by Newell Rubbermaid). Then, after wiping this with a tissue (manufactured by Daio Paper Industries Co., Ltd., Erielle) 10 times to draw a circle, the surface was visually observed and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
○: The stains were removed after 2 to 5 wipes.
:: Weak and weak. The stains were gone after wiping 6 to 10 times.
X: Dirt remained even after wiping 10 times without peeling.

<Scratch resistance>
Place a melamine sponge (trade name: Play-off) on tap water surface with a tap water, 10,000 reciprocate slides with a load of 300 gf / cm ² (sliding stroke: 3 cm, sliding speed: 6 cm / s ), The scratch resistance was evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
○: There was no change in appearance such as damage or cloudiness.
X: There was a change in appearance such as damage or cloudiness.

<Chemical resistance>
After moistening with acetone for 10 minutes, the chemical resistance was evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
○: There was no change in the appearance.
X: There were changes in appearance such as sore or cloudiness.

<Coat adhesion>
After exposure to the following environment, each was subjected to a crosscut adhesion test in accordance with JIS K5600-5-6 (crosscut test method), and coat adhesion was evaluated according to the following evaluation criteria.
[Exposure conditions]
1. Exposure to steam from hot water at 80 ° C for 5 minutes.
2. Immerse in mold killer (Johnson & Johnson) for 1 hour.
〔Evaluation criteria〕
○: It did not peel off under any of the conditions.
X: Peeled off under one or more conditions.

<Pencil hardness>
It measured according to JIS K 5600-5-4.

Example 1
<Base material>
A mirror (a mirror formed by depositing silver on a float plate glass, an average thickness of 5 mm) was used as a substrate.

<Formation of primer layer>
The following resin composition for primer layer formation was apply | coated on the said mirror so that the average thickness after drying and hardening might be set to 2 micrometers to the said base material. After application, it was dried in an oven at 80 ° C. for 3 minutes. The primer layer was obtained by irradiating ultraviolet rays with an irradiation amount of 500 mJ / cm ² in an air atmosphere using a high pressure mercury lamp.

-Resin composition for forming primer layer-
· UT 5181 (manufactured by Nippon Gosei Co., Ltd.) 65.0 parts by mass · EBECRYL 40 (manufactured by Daicel Ornex Co., Ltd.) 35.0 parts by mass · UV 3500 (manufactured by BYK) 0.05 parts by mass · Irgacure 184 D (manufactured by BASF) 3.0 parts by mass-Solvent PGME (propylene glycol monomethyl ether) 900 parts by mass

The details of the material are as follows.
· UT 5181: Urethane acrylate · Irgacure 184D: 1-hydroxy-cyclohexyl-phenyl-ketone · EBECRYL 40: pentaerythritol alkoxy tetraacrylate · UV 3500: silicone surfactant

<Formation of functional layer>
Next, on the primer layer, an active energy ray-curable resin composition having the following composition was applied so as to have an average thickness of 35 μm after drying and curing. After application, it was dried in an oven at 80 ° C. for 2 minutes. An anti-fogging anti-soiling coating layer (functional layer) was cured by irradiating ultraviolet rays with a dose of 500 mJ / cm ² in a nitrogen atmosphere using a metal halide lamp to obtain an anti-fogging anti-staining laminate.

-Active energy ray curable resin composition [Resin composition for forming antifogging antifouling coating layer (functional layer)]-
· SR 9035 (made by Sartmar) 67.9 parts by mass · EBECRYL 40 (made by Daicel Ornex Co., Ltd.) 29.1 parts by mass · Optool DAC-HP (manufactured by Daikin Industries, Ltd.) 0.1 parts by mass · Irgacure 184 D (BASF Made by company) 2.9 parts by mass ・ PGME (propylene glycol monomethyl ether) 100 parts by mass

The details of the material are as follows.
· SR 9035: Ethoxylated (15) trimethylolpropane triacrylate · Optool DAC-HP: UV curable perfluoropolyether (PFPE)

  The above evaluation was performed on the obtained antifogging antifouling laminate. The results are shown in Table 3-1.

(Example 2)
An anti-fogging anti-soiling laminate was obtained in the same manner as in Example 1 except that an anti-fogging anti-soiling coating layer (functional layer) was formed using an active energy ray-curable resin composition having the following composition.

-Active energy ray curable resin composition [Resin composition for forming antifogging antifouling coating layer (functional layer)]-
· SR 9035 (Sartmar Co., Ltd.) 67.9 parts by mass · EBECRYL 40 (manufactured by Daicel Ornex Co., Ltd.) 29.1 parts by mass · Optool DAC-HP (manufactured by Daikin Industries, Ltd.) 0.1 parts by mass · UV 3500 (BYK Co.) Made of 0.05 parts by weight Irgacure 184D (manufactured by BASF) 2.9 parts by weight PGME (propylene glycol monomethyl ether) 100 parts by weight

  The obtained antifogging antifouling laminate was evaluated in the same manner as in Example 1. The results are shown in Table 3-1.

(Comparative example 1)
In the same manner as in Example 1 except that a primer layer was formed using an active energy ray curable resin composition of the following composition, and the average thickness of the antifogging antifouling coat layer (functional layer) was changed to 45 μm, An antifogging antifouling laminate was obtained.

Active energy ray curable resin composition (resin composition for forming primer layer)
-UT 5181 (manufactured by Nippon Gosei Co., Ltd.) 65.0 parts by mass-EBECRYL 40 (manufactured by Daicel Ornex Co., Ltd.) 35.0 parts by mass-Irgacure 184D (manufactured by BASF) 3.0 parts by mass-Solvents PGME (propylene glycol monomethyl Ether) 900 parts by mass

  The obtained antifogging antifouling laminate was evaluated in the same manner as in Example 1. The results are shown in Table 3-1.

(Comparative example 2)
An antifogging antifouling laminate was obtained in the same manner as in Example 1 except that the average thickness of the antifogging antifouling coat layer was 45 μm.

  The obtained antifogging antifouling laminate was evaluated in the same manner as in Example 1. The results are shown in Table 3-1.

(Comparative example 3)
A commercially available vanity-use antifog mirror was evaluated. The results are shown in Table 3-1.

(Example 3)
An anti-fogging anti-soiling laminate was obtained in the same manner as in Example 1 except that a primer layer was formed using an active energy ray-curable resin composition having the following composition.

Active energy ray curable resin composition (resin composition for forming primer layer)
· UT 5181 (manufactured by Nippon Gosei Co., Ltd.) 65.0 parts by mass · EBECRYL 40 (manufactured by Daicel Ornex Co., Ltd.) 35.0 parts by mass · UV 3500 (manufactured by BYK) 0.01 parts by mass · Irgacure 184 D (manufactured by BASF) 3.0 parts by mass-Solvent PGME (propylene glycol monomethyl ether) 900 parts by mass

  The obtained antifogging antifouling laminate was evaluated in the same manner as in Example 1. The results are shown in Table 3-1.

(Example 4)
An anti-fogging anti-soiling laminate was obtained in the same manner as in Example 1 except that a primer layer was formed using an active energy ray-curable resin composition having the following composition.

Active energy ray curable resin composition (resin composition for forming primer layer)
· UT 5181 (manufactured by Nippon Gosei Co., Ltd.) 65.0 parts by mass · EBECRYL 40 (manufactured by Daicel Ornex Co., Ltd.) 35.0 parts by mass · UV 3500 (manufactured by BYK) 1.0 parts by mass · Irgacure 184 D (manufactured by BASF) 3.0 parts by mass-Solvent PGME (propylene glycol monomethyl ether) 900 parts by mass

  The obtained antifogging antifouling laminate was evaluated in the same manner as in Example 1. The results are shown in Table 3-1.

(Examples 5 to 9)
In Example 1, the resin composition for forming a primer layer, the resin composition for forming a functional layer, and the average thickness of the primer layer and the average thickness of the functional layer are described in Table 2-2. The antifogging anti-soiling laminate was obtained in the same manner as in Example 1 except that the average thickness of the product, the resin composition for forming a functional layer, the primer layer, and the average thickness of the functional layer was used.
The obtained antifogging antifouling laminate was evaluated in the same manner as in Example 1. The results are shown in Table 3-2.

  Resin compositions for forming a primer layer in Examples 1 to 4 and Comparative Examples 1 to 3, resin compositions for forming a functional layer, and average thicknesses of the primer layers and average thicknesses of the functional layers are summarized in Table 2-1. The

In Tables 2-1 and 2-2, the unit of the compounding amount is parts by mass.
The details of the unexplained materials in Tables 2-1 and 2-2 are as follows.
· KP 323: Shin-Etsu Chemical Co., Ltd. silicone-based surfactant · UV 3510: BYK manufactured silicone-based surfactant · KY-1203: Shin-Etsu Chemical Co., Ltd. water repellent monomer

In Examples 1 to 9, the distortion of the image was small at the end of the mirror as compared to the comparative example. Among the examples, in Example 2, the height (h) of the convex portion is 5.5 mm or less, the width (w) of the convex portion is 6.0 mm or less, and the length between the end side and the top side (l The distortion of the image at the end of the mirror was not particularly noticeable, since it was less than 3.0 mm.
On the other hand, in Comparative Examples 1 to 3, distortion of the image was anxious at the end.

  The laminate of the present invention includes glass windows, refrigerated / freezeable showcases, window materials such as windows of cars, mirrors of water such as bathrooms and washrooms, mirrors such as automobile side mirrors, floors and walls of bathrooms, and solar panel surfaces. It can be used as a security surveillance camera or the like, and can also be suitably used as a mirror for a bathroom or a washbasin.

11 substrate 12 primer layer 13 functional layer 14 metal layer 15 back surface protective layer

<< Height of convex part >>
The height of the convex portion is at 10μm or less, preferably 8.0 .mu.m or less, and more preferably 7.0 .mu.m or less, and particularly preferably 5.5 mu m. There is no restriction | limiting in particular in the lower limit of the height of the said convex part, According to the objective, it can select suitably, For example, the height of the said convex part may be 1.0 micrometer or more, or 2. It may be 0 μm or more, or 4.0 μm or more.

In Examples 1 to 9, the distortion of the image was small at the end of the mirror as compared to the comparative example. Among the examples, in Example 2, the height (h) of the protrusions is 5.5 μm or less, the width (w) of the protrusions is 6.0 mm or less, and the length between the end side and the top side The distortion of the image at the end of the mirror was not particularly noticeable because (l) was less than 3.0 mm.
On the other hand, in Comparative Examples 1 to 3, distortion of the image was anxious at the end.

Claims (19)

A laminate comprising a substrate, a primer layer on the substrate, and a functional layer having at least one of antifogging and antifouling functions on the primer layer,
The surface on the functional layer side of the end portion of the laminate has a convex portion having a top side portion along the end side of the end portion,
The height of the protrusion is 10 μm or less, the width of the protrusion is 15 mm or less, and the edge and the top side in a cross section orthogonal to the direction of the edge and the surface direction of the surface The laminated body characterized in that the length between and is 5.0 mm or less.   The layered product according to claim 1 whose height of said convex part is 1 micrometer-10 micrometers.   The layered product according to any one of claims 1 to 2 whose pure water contact angle of the surface of said functional layer is 80 degrees or more, and whose hexadecane contact angle is 35 degrees or more.   The laminate according to any one of claims 1 to 3, wherein the average thickness of the primer layer is 0.5 m to 5 m.   The average thickness of the said functional layer is 10 micrometers or more, The laminated body in any one of Claim 1 to 4.   The laminated body according to any one of claims 1 to 5, wherein a dynamic friction coefficient of the functional layer is 0.40 or less. The primer layer is a cured product of an active energy ray curable resin composition,
The laminate according to any one of claims 1 to 6, wherein the active energy ray curable resin composition contains a surfactant.   The laminate according to claim 7, wherein the surfactant is at least one of a silicone surfactant and a fluorosurfactant.   Content of the said surfactant in the said active energy ray curable resin composition is 0.0001 mass%-5.0 mass% with respect to the non volatile matter of the said active energy ray curable resin composition. The laminated body in any one of 7 to 8.   An article having the laminate according to any one of claims 1 to 9 on its surface.   11. The article of claim 10 which is a mirror.   The article according to claim 11, which is at least one of a bathroom and a sink.   The image of the wire mesh is not distorted when the image of the wire mesh is evaluated by visual observation, standing with a 1 cm-wide wire mesh standing at a position 1 m away from the mirror surface in the normal direction. The article according to any of the above. It is an active energy ray curable resin composition used for formation of the said primer layer of the laminated body in any one of Claim 1 to 6, Comprising:
An active energy ray-curable resin composition comprising a surfactant.   The active energy ray curable resin composition according to claim 14, wherein the surfactant is at least one of a silicone surfactant and a fluorine surfactant.   The content of the said surfactant is 0.0001 mass%-5.0 mass% with respect to the non volatile matter of the said active energy ray curable resin composition, The activity in any one of Claim 14 to 15 Energy ray curable resin composition. It is a manufacturing method of the layered product according to any one of claims 1 to 6,
A method of producing a laminate comprising a primer layer forming step of applying an active energy ray curable resin composition containing a surfactant onto the substrate and curing it to form the primer layer. .   The method for producing a laminate according to claim 17, wherein the surfactant is at least one of a silicone surfactant and a fluorosurfactant.   Content of the said surfactant in the said active energy ray curable resin composition is 0.0001 mass%-5.0 mass% with respect to the non volatile matter of the said active energy ray curable resin composition. The manufacturing method of the laminated body in any one of 17-18.