Laminate

Abstract

To provide a laminate having a certain degree of light transmission, water repellency and anti-glare property.SOLUTION: There is provided a laminate, comprising a filler particle-containing resin layer and a functional layer in this order on a substrate, wherein the filler particle-containing resin layer contains a coating resin and filler particles having an average particle diameter of 3 μm or more and 200 μm or less dispersed in the coating resin, and the functional layer is formed by laminating hydrophobic oxide fine particles having an average primary particle diameter of 3 nm to 100 nm, and a lamination amount of the hydrophobic oxide fine particles is 0.3 g / m2 to 20.0 g / m2.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a laminate having water repellency.

Background Art

[0002] Structures such as roofs, windows, and solar panels are soiled by the accumulation of various contaminants such as pollen, vehicle dust, sand, dust, and other PM2.5 along with snow and rain. Therefore, frequent cleaning is required to maintain their functions and aesthetics.

[0003] To reduce the frequency of such cleaning, methods of laminating a water-repellent paint or sheet on structures such as roofs, windows, and solar panels to allow contaminants to naturally slide off along with snow and rain have been studied. For example, Patent Document 1 discloses an anti-snow adhesion paint comprising a mixed composition of low molecular weight tetrafluoroethylene powder and at least one resin selected from fluororesin, acrylic silicone resin, polyester resin, and silicone resin.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in the technology of the above-mentioned literature, when the snow-preventive paint is applied to the surface of a window, a solar panel, etc. and dried, the light transmittance decreases. In the case of a window, there is a risk that the visibility of the outside scenery will decrease and the interior will become dark. Also, in the case of a solar panel, the amount of light irradiated onto the solar cell element will be reduced, and there is a risk that the power generation amount will be significantly impaired. Furthermore, roofs, windows, solar panels, etc. may cause people outside to feel dazzled due to the reflection of sunlight on their surfaces. If an anti-glare member such as a glare film is attached to the surface of the snow-preventive paint to suppress this, the light transmittance will be further impaired, and at the same time, water repellency cannot be obtained, and it becomes impossible to suppress the adhesion of snow, rain, dirt, etc.

[0006] In addition, commercially available water-repellent films are only those with poor light transmittance or without anti-glare properties, and there are problems in applying them to structures such as roofs, windows, solar panels, etc.

[0007] Therefore, an object of the present invention is to provide a laminate having a certain light transmittance, water repellency, and anti-glare properties.

Means for Solving the Problems

[0008] In view of the above problems, the inventors conducted various studies and found that the above problems can be solved by a laminate having the following configuration.

[0009] That is, the laminate of the present invention includes, in order on a base material, a resin layer containing filler particles and a functional layer. The resin layer containing filler particles contains a coating resin and filler particles having an average particle diameter of 3 μm or more and 200 μm or less dispersed in the coating resin. The functional layer is composed of hydrophobic oxide fine particles having an average primary particle diameter of 3 nm or more and 100 nm or less laminated thereon, and the laminated amount of the hydrophobic oxide fine particles is 0.3 g / m 2 or more and 20.0 g / m 2 or less.

[0010] Due to the laminate of the present invention having the above configuration, while having a certain light transmittance, it has water repellency and anti-glare properties. That is, even when pasted on the surface of a window, a solar panel, etc., it does not impair the visibility outdoors from the window or the power generation performance of the solar panel, prevents dirt and the like from adhering due to water repellency, and can further suppress the glare caused by light reflection. In the present invention, a certain light transmittance means that the light transmittance at a wavelength of 555 nm measured by an ultraviolet-visible-infrared spectrophotometer is 70% or more.

[0011] It is preferable that the laminate has a light transmittance of 70% or more at a wavelength of 555 nm. It is preferable that the laminate has a 60-degree gloss value of 50 or less.

[0012] It is preferable that the laminate has a filling particle occupancy ratio of 0.05 or more and 0.90 or less in the projected area in the plan view on the side where the functional layer of the filling particle-containing resin layer is laminated. The laminate preferably has a weight per unit area of the filling particle-containing resin layer of 1 g / m 2 or more and 200 g / m 2 or less.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0014] The laminate of the present invention includes a filling particle-containing resin layer and a functional layer in this order on a substrate. The filling particle-containing resin layer contains a coating resin and filling particles having an average particle diameter of 3 μm or more and 200 μm or less dispersed in the coating resin. The functional layer is composed of hydrophobic oxide fine particles having an average primary particle diameter of 3 nm or more and 100 nm or less laminated thereon, and the laminated amount of the hydrophobic oxide fine particles is 0.3 g / m 2 or more and 20.0 g / m2 It is characterized by the following. The following constituent elements will be described in detail.

[0015] Fig. 1 shows a schematic cross-sectional view as an example of the layer structure according to an embodiment of the laminate of the present invention. As the basic structure of the laminate 10, a filler particle-containing resin layer 12 and a functional layer 13 are sequentially laminated on a base material 11. In Fig. 1, these layers are laminated so as to be in contact with each other. And the functional layer 13 is arranged as the outermost layer (the outermost surface layer).

[0016] The filler particle-containing resin layer 12 contains a plurality of filler particles 12b in a coating film resin 12a. Due to these filler particles, the filler particle-containing resin layer 12 has an uneven shape formed on its surface. And an uneven shape is also formed on the surface of the functional layer 13 so as to follow this uneven shape.

[0017] The functional layer 13 is a layer having a water-repellent property function constituted by hydrophobic oxide fine particles 13a.

[0018] In this way, together with the water-repellent property of the hydrophobic oxide fine particles 13a themselves, high water repellency and durability can be exhibited due to the uneven shape on the surface of the functional layer 13. By having high water repellency, dirt and the like can be washed away together with rain and snow. The durability mentioned here refers to the difficulty of detachment of the hydrophobic oxide fine particles from the functional layer 13. The laminate of the present invention has an uneven shape due to the filler particles 12b contained in the filler particle-containing resin layer 12, and by holding the hydrophobic oxide fine particles 13a on the surface of the filler particle-containing resin layer 12, even if there is external damage such as friction, it only reaches a part of the surface of the filler particle-containing resin layer 12, that is, the hydrophobic oxide fine particles 13a are difficult to detach from the laminate and high water repellency can be maintained. Hereinafter, each layer and the like will be described in more detail.

[0019] (Laminate)

[0020] The laminate of the present invention is applicable to products such as windows and solar panels, as well as traffic signals, road signs, antennas, display boards, daily necessities (glasses, rain gear, bags, etc.), building materials (roofs, wallpapers, floor materials, ceiling materials, tiles, etc.), sports goods, clothing (hats, shoes, gloves, coats, etc.), structures (walls of buildings, bridges, towers, etc.), transportation equipment (outer surfaces of bodies of airplanes, cars, motorcycles, trains, ships, etc.), and playground equipment. In particular, since the laminate of the present invention has a certain light transmittance, antiglare property, and water repellency, it can be preferably applied to display surfaces of display devices and members such as traffic signals and road signs, windows, and solar panels.

[0021] (Base material)

[0022] In the present invention, the base material serves as a support member for laminating the filler particle-containing resin layer and the functional layer, and examples thereof include sheet-like, film-like, and plate-like forms. The material of such a base material is not particularly limited, and examples thereof include at least one of resin films, resin sheets, paper, non-woven fabrics, synthetic papers, rubbers, metal materials such as metal plates, metal foils, and metal films (including alloys), inorganic materials such as glass and ceramics, and composite materials containing these.

[0023] The thickness of the base material is not particularly limited, but it is preferably, for example, 3 μm or more. If it is thinner than 3 μm, there is a risk that it may easily wrinkle or tear when pasted on windows, solar panels, etc. There is no problem as long as the base material is thick, and in some cases, the base material itself is a building and its thickness cannot be defined.

[0024] When the substrate contains a resin, acrylic resin, polystyrene, ABS resin, vinyl chloride resin, polyethylene resin, polypropylene resin, polyamide resin, polycarbonate, polyacetal, fluororesin, silicone resin, polyester resin, etc., as well as blend resins thereof, copolymers containing combinations of monomers constituting these, modified resins, etc. can be used. As the thermosetting resin, epoxy resin, phenol resin, polyester resin, urea resin, melamine resin, diallyl phthalate resin, silicone resin, vinyl ester resin, polyimide, polyurethane, blend resins thereof, copolymers containing combinations of monomers constituting these, modified resins, etc. can be used. As the active energy ray curable resin, it is preferably one or more resins selected from the group consisting of radical polymerization type acrylic resins, cationic polymerization type epoxy resins, etc. In particular, from the viewpoints of light transmissivity, weather resistance, etc., polyethylene terephthalate resin or acrylic resin is preferable.

[0025] Note that the substrate may be provided with an anchor coat layer for ensuring the adhesion between the substrate and the filler particle-containing layer. As the anchor coat layer, for example, various resins, silane coupling agents, adhesives, etc. are preferably used.

[0026] (Filler particle-containing resin layer)

[0027] The filler particle-containing resin layer contains a coating film resin and filler particles. The content of the coating film resin in the filler particle-containing resin layer varies depending on, for example, the type of the coating film resin or filler particles used, the presence or absence of additives, etc., but is usually preferably 10% by weight or more and 95% by weight or less, particularly preferably 30% by weight or more and 90% by weight or less, and more preferably 50% by weight or more and 85% by weight or less.

[0028] As the resin constituting the coating film resin, known resins can be adopted. Examples of the resin include thermoplastic resins, thermosetting resins, and active energy ray curable resins. Among these, for thermosetting resins, for example, acrylic resins, polystyrene, ABS resins, vinyl chloride resins, polyethylene resins, polypropylene resins, polyamide-based resins, polycarbonates, polyacetals, fluorine-based resins, silicon resins, polyester-based resins, etc. In addition, blend resins thereof, copolymers including combinations of monomers constituting these, modified resins, etc. can be used. As thermosetting resins, epoxy resins, phenol resins, polyester resins, urea resins, melamine resins, diallyl phthalate resins, silicon resins, vinyl ester resins, polyimides, polyurethanes, blend resins thereof, copolymers including combinations of monomers constituting these, modified resins, etc. can be used. As active energy ray curable resins, radical polymerization type acrylic resins, cationic polymerization type epoxy resins, etc. can be used.

[0029] In the coating film resin, other components may be contained within a range that does not prevent the effects of the present invention. For example, additives such as dispersants, colorants, antioxidants, pigments, dyes, ultraviolet absorbers, etc. can be mentioned.

[0030] The filler particles contained in the filler particle-containing resin layer form irregularities on the surface of the filler particle-containing resin layer and are used not only to enhance water repellency but also to improve durability. Such filler particles may be composed of either organic components or inorganic components, or may be mixtures thereof.

[0031] Examples of the inorganic components used as the filling particles include metals such as aluminum, copper, iron, titanium, silver, and calcium, alloys or intermetallic compounds containing these metals, oxides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, and iron oxide, inorganic acid salts or organic acid salts such as calcium phosphate and calcium stearate, glass, ceramics such as aluminum nitride, boron nitride, silicon carbide, and silicon nitride, etc. Examples of the organic components include organic polymer components (or resin components) such as acrylic resins, urethane resins, melamine resins, amino resins, epoxy resins, polyethylene resins, crosslinked polymethyl methacrylate resins, polystyrene resins, polypropylene resins, polyester resins, cellulose resins, vinyl chloride resins, polyvinyl alcohol, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene-ethyl acrylate copolymers, polyacrylonitrile, and polyamides.

[0032] Among these, from the viewpoints of light transmissibility and water repellency, at least one of crosslinked polymethyl methacrylate, polyethylene fine particles, acrylic resin particles, silica particles, calcium phosphate particles, carbon powder, fired calcium particles, unfired calcium particles, calcium stearate particles, etc. can be preferably used as the filling particles.

[0033] In the present invention, the materials of the filling particles may be the same or may be mixed particles of different materials. Also, the shape of the filling particles is not limited and may be any of, for example, spherical, ellipsoidal of revolution, irregular shape, teardrop shape, flat shape, hollow shape, porous shape, etc.

[0034] In the present invention, the filled particles have an average particle diameter of 3 μm or more and 200 μm or less. This is because if the filled particles are smaller than 3 μm, an uneven structure suitable for retaining the hydrophobic oxide fine particles in the coating film cannot be formed, and if they are larger than 200 μm, they will detach from the coating film or the light transmittance will decrease. The average particle diameter of the filled particles can be measured by observing a cross-section of the laminate using a field emission scanning electron microscope (FE-SEM). Specifically, when the particle shape is spherical, its diameter is used, and when it is non-spherical, the average value of the longest diameter and the shortest diameter is regarded as the diameter. The average particle diameter is the average of the diameters of 100 arbitrarily selected particles observed by a scanning electron microscope or the like.

[0035] The content of the filled particles is preferably 1 part by weight or more and 500 parts by weight or less with respect to 100 parts by weight of the coating resin. If the content of the filled particles is less than 1 part by weight with respect to 100 parts by weight of the coating resin, high water repellency and durability may not be obtained depending on the use environment. Further, if the content of the filled particles exceeds 500 parts by weight with respect to 100 parts by weight of the coating resin, the light transmittance of the laminate may decrease depending on the type and size of the filled particles.

[0036] In the projected area in the plan view on the side where the functional layer of the filled particle-containing resin layer is laminated, the ratio of the occupied area of the filled particles to the total area of the filled particle-containing resin layer (hereinafter also referred to as the filled particle occupancy ratio) is preferably 0.05 or more and 0.90 or less.

[0037] Since the filled particle occupancy ratio is the area ratio between the surface of the filled particle-containing resin layer and the filled particles in the plan view on the side where the functional layer of the filled particle-containing resin layer is laminated, strictly speaking, the surface of the filled particle-containing resin layer before the functional layer is laminated is more accurate. However, it can also be obtained by removing the functional layer after the functional layer is laminated.

[0038] As a method for removing the functional layer from the laminate, various methods can be used. For example, specifically, a test piece of the laminate is immersed in a beaker filled with isopropyl alcohol (IPA), ethanol, or the like, and the beaker is set in an ultrasonic cleaner to remove the functional layer. Alternatively, the functional layer can be removed by applying IPA or ethanol in a circulating manner to the test piece.

[0039] After the functional layer is removed from the laminate, it is thoroughly dried, and the surface of the filler particle-containing resin layer is observed with a microscope such as an optical microscope or a scanning electron microscope (SEM). In the surface observation, it is preferable to use a magnification such that about 100 to 1000 filler particles enter one field of view. A micrograph is taken in such a field of view and imported into image analysis software such as ImageJ from NIH, for example, to calculate the area of a predetermined region and the total area of all the filler particles in this predetermined region. The predetermined region may be the entire field of view of the micrograph or a region cut out from a part of the micrograph. If there are 100 or more filler particles in the entire field of view of the micrograph, from the viewpoint of measurement simplicity, a part of the micrograph may be cut out so that the number of filler particles is less than 100 for measurement. However, if the number of filler particles contained in the predetermined region is too small, there is a risk that the filler particle occupancy ratio cannot be correctly calculated, so the number of filler particles contained in the predetermined region is preferably 10 or more.

[0040] In addition, when surrounding the filler particles within a selection range to calculate the total area of the filler particles by image analysis software, if the contour of the filler particles is blurred, it is preferable to adopt the outermost line. Also, when the filler particles straddle the predetermined region, it is preferable to measure only the portion that enters the predetermined region and not measure the portion that protrudes outside the predetermined region. Furthermore, when a plurality of filler particles are stuck together or overlapping, there is no need to decompose and analyze the filler particles in order to calculate the projected area on the micrograph. It is preferable to measure the range surrounded by the overall contour as it is in the stuck-together or overlapping state.

[0041] After calculating the area of a predetermined region and the total area of all the filled particles in the predetermined region, the value obtained by dividing the total area of all the filled particles in the predetermined region by the area of the predetermined region is the filled particle occupancy ratio. It is preferable to change the field of view, the laminate sample, the predetermined region, etc., calculate the filled particle occupancy ratio with the number of samples n = 5, and obtain the average thereof.

[0042] If the filled particle occupancy ratio is less than 0.05, it becomes difficult to form an appropriate uneven structure capable of retaining the hydrophobic oxide fine particles in the coating film. If the filled particle occupancy ratio is more than 0.90, at least a part of the filled particles may detach from the coating film or the light transmittance may decrease.

[0043] The method of incorporating the filled particles into the coating film resin is not particularly limited. For example, a method of blending and coating the filled particles in a raw material (also referred to as a composition containing a resin or a matrix) for forming a filled particle-containing resin layer can be mentioned. The mixing method may be either dry mixing or wet mixing. Generally, since the main component of the raw material for forming the resin layer consists of a resin or a monomer or oligomer constituting the resin, a solvent, a crosslinking agent, etc. as required, the filled particles may be added and mixed in these mixtures.

[0044] The method of forming the filled particle-containing resin layer is not particularly limited. For example, it can be formed by a method including a step of applying a coating liquid containing a coating film resin, filled particles, and a solvent to a substrate.

[0045] As the coating liquid, a dispersion liquid in which the above coating film resin and filled particles are dispersed can be preferably used. In this case, as long as the effects of the present invention are not impaired, a part of these may be dissolved in the solvent.

[0046] The solvent contained in the coating liquid is not particularly limited. In addition to water, for example, organic solvents such as alcohol (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol, normal pentane, normal hexane, hexyl alcohol, butyl acetate, and ethyl acetate can be appropriately selected. At this time, a small amount of dispersant, colorant, anti-settling agent, viscosity modifier, etc. can also be used in combination. In this case, the dispersion amount of the solid content with respect to the solvent may usually be about 1 g / L to 500 g / L.

[0047] For the method of applying such a coating liquid to a substrate, known methods such as roll coating, gravure coating, bar coating, doctor blade coating, brush coating, spraying, powder electrostatic method, etc. can be adopted.

[0048] After applying the coating liquid to the substrate, it is preferably followed by a drying (including curing) process if necessary. For thermoplastic resins and thermosetting resins, when drying, either natural drying or forced drying (heat drying) may be used, but industrially, forced drying is preferably used. The drying temperature is not limited as long as it does not affect the filled particle-containing resin layer, but usually it is preferably 100 °C or lower, particularly 20 °C or higher and 60 °C or lower. If the UV curable resin contains a solvent, it can be cured by UV irradiation after passing through the drying process.

[0049] The thickness of the filler particle-containing resin layer laminated on the substrate is preferably about 5 μm to 200 μm, more preferably about 10 μm to 100 μm, in order to obtain antiglare properties and light transmittance. When the substrate is thin and uniform such as a film, this film thickness can be measured using a micro gauge. Specifically, the total thickness of the substrate and the film thickness is calculated as the average value of six measurement data obtained by measuring 10 times and excluding the maximum value, the second largest value, the minimum value, and the second smallest value. Then, the thickness of only the film thickness can be calculated by subtracting the thickness of the substrate from the total thickness of the substrate and the film thickness. When the substrate is thick and has large surface irregularities and a micro gauge cannot be used, the cross section is observed by FE-SEM, and the average of 100 measurements of the thickness of the filler particle-containing layer is calculated as the film thickness.

[0050] (Functional layer) The functional layer is laminated on the surface of the filler particle-containing resin layer. As a preferred example, it is arranged as the outermost surface layer of the laminate of the present invention.

[0051] In the present invention, for example, as shown in FIG. 1, it is preferable that a plurality of hydrophobic oxide fine particles 13a (particle groups) are laminated to form a functional layer. The surface on which the nano-sized fine particles are laminated forms nano-sized irregularities and has high water repellency.

[0052] The hydrophobic oxide fine particles usually have an average primary particle diameter of 3 nm or more and 100 nm or less, preferably 5 nm or more and 50 nm or less, more preferably 5 nm or more and 30 nm or less. By setting the average primary particle diameter of the hydrophobic oxide fine particles within the above range, the hydrophobic oxide fine particles are in an appropriate aggregated state, and gases such as air can be held in the voids in the aggregates. As a result, excellent water repellency, that is, an antifouling effect can be obtained. That is, since this aggregated state is maintained even after being laminated on the filler particle-containing layer, excellent water repellency (antifouling effect) can be exhibited.

[0053] In the present invention, the average primary particle diameter can be measured by observing and measuring the surface of the laminate using a scanning electron microscope (FE-SEM). When the resolution of the scanning electron microscope is low, other electron microscopes such as a transmission electron microscope may be used in combination. Specifically, when the particle shape is spherical, its diameter is used; when the particle shape is non-spherical, the average value of the longest diameter and the shortest diameter is regarded as the diameter. The average of the diameters of 100 arbitrarily selected particles observed by a scanning electron microscope or the like is defined as the average primary particle diameter.

[0054] In addition, the specific surface area (BET method) of the hydrophobic oxide fine particles is not particularly limited, but is usually about 50 m 2 / g to 300 m 2 / g, and particularly preferably 100 m 2 / g to 250 m 2 / g.

[0055] The hydrophobic oxide fine particles are not particularly limited as long as they have hydrophobicity, and those hydrophobized by surface treatment may also be used. For example, fine particles obtained by subjecting hydrophilic oxide fine particles to surface treatment with a silane coupling agent or the like to make the surface state hydrophobic can also be used. The type of oxide is not limited as long as it has hydrophobicity. For example, at least one of silica (silicon dioxide), alumina, titania, etc. can be used. These can be known or commercially available products. For example, as silica, product names such as "AEROSIL R972", "AEROSIL R972V", "AEROSIL R972CF", "AEROSIL R974", "AEROSIL RX200", "AEROSIL RY200" (manufactured by Nippon Aerosil Co., Ltd.), "AEROSIL R202", "AEROSIL R805", "AEROSIL R812", "AEROSIL R812S" (manufactured by Nippon Aerosil Co., Ltd.) can be mentioned. As titania, product names such as "AEROXIDE TiO2 T805" (manufactured by Nippon Aerosil Co., Ltd.) can be exemplified.

[0056] Examples of alumina include fine particles obtained by treating a product name "AEROXIDE Alu C" (manufactured by Nippon Aerosil Co., Ltd.) with a silane coupling agent to make the particle surface hydrophobic.

[0057] Among these, hydrophobic silica fine particles can be preferably used. In particular, hydrophobic silica fine particles having a trimethylsilyl group on the surface are preferable in terms of obtaining more excellent non-adhesiveness. Commercially available products corresponding to this include, for example, the above-mentioned "AEROSIL R812", "AEROSIL R812S" (both manufactured by Nippon Aerosil Co., Ltd.).

[0058] The adhesion amount (coating amount after drying) of the hydrophobic oxide fine particles in the functional layer is 0.3 g / m 2 or more and 20.0 g / m 2 or less. More preferably, the adhesion amount (coating amount after drying) of the hydrophobic oxide fine particles in the functional layer is 0.5 g / m 2 or more and 10.0 g / m 2 or less. By setting within the above range, high waterproof and antifouling performances can be obtained, and it is more advantageous in terms of suppressing the dropout of the hydrophobic oxide fine particles, ensuring light transmittance, and exhibiting antiglare properties.

[0059] When applying the hydrophobic oxide fine particles to the uneven layer surface of the resin layer containing the filler particles, the hydrophobic oxide fine particles may be directly sprayed or applied (dry method), or may be applied by coating a dispersion liquid obtained by dispersing the hydrophobic oxide fine particles in a solvent (wet method). In the present invention, from the viewpoint of easily obtaining an industrially uniform coating film (functional layer) and easily obtaining high water repellency, it is preferable to adopt the latter wet method.

[0060] When using the above-mentioned dispersion liquid, the solvent used in the dispersion liquid can be appropriately selected from organic solvents such as alcohol (ethanol), cyclohexane, toluene, butyl acetate, ethyl acetate, acetone, isopropyl alcohol (IPA), propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol, normal propyl alcohol, normal pentane, normal hexane, hexyl alcohol, etc.

[0061] At this time, within the range that does not interfere with the effects of the present invention, a small amount of dispersant, colorant, anti-settling agent, viscosity modifier, etc. can also be used in combination. The dispersion amount of the hydrophobic oxide fine particles with respect to the solvent is usually about 10 g / L to 300 g / L (liter), preferably about 30 g / L to 100 g / L.

[0062] The method of coating the dispersion liquid is not limited either. For example, known methods such as roll coating, gravure coating, bar coating, doctor blade coating, brush coating, spraying, inkjet printing, screen printing, dropping method, electrostatic coating, etc. can be adopted. After coating, it can be appropriately dried at room temperature to about 150 °C.

Examples

[0063] Examples and comparative examples are shown below to more specifically explain the features of the present invention. However, the scope of the present invention is not limited to the examples.

[0064] [Example 1]

[0065] First, a resin layer containing filled particles was formed on a substrate (PET film, thickness 50 μm). Specifically, in order to form the resin layer containing filled particles, an acrylic vinyl polyester resin paint (product name "SK8730BA-H1", manufactured by Sakurami Chemical Co., Ltd., resin solid content: 31.6 wt%) was used as the coating resin, and crosslinked polymethyl methacrylate with an average particle diameter of 5 μm (product name "MBX-5", manufactured by Sekisui Chemical Co., Ltd.) was used as the filled particles. The above-mentioned resin solid content and filled particles were mixed and dispersed so that the weight ratio became 100 / 100, and diluted with butyl acetate to a viscosity suitable for coating as appropriate to prepare a coating solution. The obtained coating solution was applied to the surface of the substrate by a bar coater so that the weight after drying was 2.4 g / m 2 and the filled particle-containing layer was produced by drying at 130°C for about 1 minute. Also, the filled particle occupancy ratio, which will be described later, was 0.47 at this time.

[0066] Next, a functional layer was formed on the resin layer containing filled particles. Specifically, a coating solution was prepared by mixing and dispersing hydrophobic silica fine particles (manufactured by Nippon Aerosil Co., Ltd., "AEROSIL R812S", average primary particle diameter = 7 nm) in ethanol so that the solid content was 5 wt%. The obtained coating solution was applied to the surface of the resin layer containing filled particles on the substrate by a bar coater so that the coating amount after drying was 2.5 g / m in terms of weight after drying 2 and the functional layer was produced by drying at 130°C for about 1 minute. In this way, a sample of a laminate having a substrate / resin layer containing filled particles / functional layer in this order was obtained.

[0067] [Example 2]

[0068] The filled particles were changed to crosslinked polymethyl methacrylate with an average particle diameter of 20 μm (product name "MBX-20", manufactured by Sekisui Chemical Co., Ltd.), and a sample of a laminate was obtained in the same manner as in Example 1 except that the resin layer containing filled particles had a weight after drying of 2.8 g / m 2 At this time, the filled particle occupancy ratio was 0.20.

[0069] [Example 3]

[0070] The filled particles were changed to crosslinked polymethyl methacrylate with an average particle diameter of 50 μm (product name "MBX-50", manufactured by Sekisui Chemical Co., Ltd.), and the resin layer containing the filled particles was 9.5 g / m as the weight after drying. 2 A sample of the laminate was obtained in the same manner as in Example 1 except for the above. The occupancy ratio of the filled particles at this time was 0.16.

[0071] [Example 4]

[0072] The filled particles were changed to crosslinked polymethyl methacrylate with an average particle diameter of 100 μm (product name "MBX-100", manufactured by Sekisui Chemical Co., Ltd.), and the resin layer containing the filled particles was 17.2 g / m as the weight after drying. 2 A sample of the laminate was obtained in the same manner as in Example 1 except for the above. The occupancy ratio of the filled particles at this time was 0.24.

[0073] [Example 5]

[0074] The filled particles were changed to crosslinked polymethyl methacrylate with an average particle diameter of 200 μm (product name "MBX-200", manufactured by Sekisui Chemical Co., Ltd.), and the resin layer containing the filled particles was 23.8 g / m as the weight after drying. 2 A sample of the laminate was obtained in the same manner as in Example 1 except for the above. The occupancy ratio of the filled particles at this time was 0.15.

[0075] [Example 6] The functional layer was 0.3 g / m as the weight after drying. 2 A sample of the laminate was obtained in the same manner as in Example 2 except for the above.

[0076] [Example 7] The functional layer was 6.3 g / m as the weight after drying. 2 A sample of the laminate was obtained in the same manner as in Example 2 except for the above.

[0077] [Example 8] The functional layer was 12.0 g / m as the weight after drying. 2 A sample of the laminate was obtained in the same manner as in Example 2 except for the above.

[0078] [Example 9]

[0079] A sample of the laminate was obtained in the same manner as in Example 2, except that the coating liquid of the resin layer containing filler particles was diluted with butyl acetate and adjusted so that the filler particle occupancy was 0.05.

[0080] [Example 10]

[0081] A sample of the laminate was obtained in the same manner as in Example 2, except that the filler particle occupancy of the resin layer containing filler particles was adjusted to 0.9 by adjusting the weight ratio of the resin solid content and the filler particles when preparing the coating liquid of the resin layer containing filler particles.

[0082] [Reference Example 1] For reference, only the 50-μm PET film used as the base material in the examples was used.

[0083] [Comparative Example 1] A general-purpose liquid crystal protection anti-glare (AG) film (manufactured by Sunwa Prime Co., Ltd., LCD-150) showing anti-glare properties was obtained.

[0084] [Comparative Example 2]

[0085] A PET film coated with HIREC300-W (manufactured by NTT Advanced Technology Corporation), which is claimed to be able to form a water-repellent coating film, with a thickness of 10 μm was obtained.

[0086] [Comparative Example 3]

[0087] The filler particles were changed to synthetic spherical silica powder (manufactured by Admatechs Co., Ltd., SO-C4) with an average particle diameter of 1 μm, and the resin layer containing filler particles was 2.5 g / m as the weight after drying 2 A sample of the laminate was obtained in the same manner as in Example 1, except for the above.

[0088] [Comparative Example 4]

[0089] The filled particles were changed to spherical phenol resin with an average particle diameter of 500 μm (manufactured by Lignite Co., Ltd., LPS-500C), and the resin layer containing the filled particles was 33.1 g / m as the dry weight. 2 A sample of the laminate was obtained in the same manner as in Example 1, except that the above was done.

[0090] [Comparative Example 5] The functional layer was 0.1 g / m as the dry weight. 2 A sample of the laminate was obtained in the same manner as in Example 2, except that the above was done.

[0091] [Comparative Example 6] The functional layer was 30.0 g / m as the dry weight. 2 A sample of the laminate was obtained in the same manner as in Example 2, except that the above was done.

[0092] [Comparative Example 7] A sample of the laminate was obtained in the same manner as in Example 2, except that the occupancy ratio of the filled particles in the resin layer containing the filled particles was 0.03.

[0093] [Comparative Example 8] A sample of the laminate was obtained in the same manner as in Example 2, except that the occupancy ratio of the filled particles in the resin layer containing the filled particles was 1.00.

[0094] [Test Example 1]

[0095] Measurement of the light transmittance was carried out for the evaluation of light transmittance. The light transmittance was measured using an ultraviolet-visible-infrared spectrophotometer measurement unit (manufactured by JASCO Corporation, V-770) and an integrating sphere. Although the total light transmittance for each wavelength was obtained, the measured value at a wavelength of 555 nm, which is the wavelength at which humans feel the brightest, was taken as the light transmittance. In addition, if the light transmittance was 70% or more, it was judged that it would not impair the visibility from the window to the outside or the power generation function of the solar panel even if it was pasted on the surface of a window or a solar panel.

[0096] [Test Example 2]

[0097] The anti-glare property was evaluated by the 60-degree gloss value measured using micro-TRI-gloss (manufactured by Tetani Co., Ltd., CAT.4563). Specifically, a completely black paper was placed under the test piece, the measurement angle was set to 60 degrees, and the average value of three measurements was taken as the measured value. The gloss value is also called the glossiness value. The larger the gloss value, the stronger the specular reflection and the higher the high gloss. Conversely, the smaller the gloss value, the lower the gloss and the higher the anti-glare property. Specifically, the inventors of the present application found that if the 60-degree gloss value is 50 or less, there is no dazzling feeling that makes one turn away, and it was considered acceptable if the 60-degree gloss value is 50 or less.

[0098] [Test Example 3]

[0099] As an evaluation of the water repellency, about 5 ml of water was intermittently dropped about 20 times from a height of 1 to 3 cm onto the same location on the surface of the laminate of each example and comparative example using a dropper. Each time a drop was made, the laminate was tilted at an angle of about 5 degrees to check whether all the water rolled off. Those in which the dropped water became spherical and rolled were marked as ○ indicating water repellency, and those in which the water repellency was lost by the 20th drop, those in which the water did not become spherical at all, or those in which the spherical water did not roll at all even when tilted were marked as ×. If it was water repellent, it was judged that it could prevent dirt. Also, those in which the water repellency was lost after about 20 drops were marked as × as being of no practical use.

[0100] [Test Example 4]

[0101] The ratio of the area of the filled particles (filled particle occupancy ratio) as the projected area in the plan view of the sample of the laminate in each example and comparative example on the side where the functional layer is laminated was determined as follows.

[0102] First, the laminates obtained in each of the examples and comparative examples were cut into pieces of 2 cm × 2 cm size to prepare test pieces. These test pieces were immersed in a beaker filled with ethanol, and the beaker was set in an ultrasonic cleaner and left for 60 minutes to remove the functional layer. Then, it was left standing at room temperature (25°C) for 10 minutes to dry, and observed with an optical microscope (VK-X3000 manufactured by Keyence Corporation) (see Fig. 2. Example of the laminate of Example 4). As a result, about 100 to 1000 filling particles were contained in one field of view. Next, a micrograph was taken, and this micrograph was imported into ImageJ of NIH. The entire field of view of the micrograph was selected with a square selection tool, and the area "A" of a predetermined region was calculated using the Measure tool. Next, all the filling particles in the predetermined region were selected using a round or freehand selection tool and the ROI MANAGER, and the area of the filling particles was calculated using the Measure tool. The Result window was displayed, and it was once saved as a CSV file from the File tab. The file was expanded with spreadsheet software, and the total area "B" of the filling particles was obtained by integrating all the values in the Area column (area of each filling particle). When surrounding the filling particles within the selection range, when the outline of the filling particles was blurred, the outermost line was adopted.

[0103] Furthermore, the value "B" of the total area of the filling particles was divided by the value "A" of the area of the predetermined region to calculate the filling particle occupancy ratio "B / A". Samples with n = 5 were taken by changing the field of view of the microscope, and the average was obtained. This average was taken as the filling particle occupancy ratio.

[0104] The average particle diameter of the filling particles used in each example is shown in Table 1 as the representative particle diameter from the catalog.

[0105] The results of the above test examples are shown in Table 1. As is clear from the results in Table 1, in each example, the light transmittance was 70% or more, the 60-degree gloss value was 50 or less, and the water repellency was ○. The reference example and each comparative example resulted in a lack of any one of these three.

[0106]

Table 1

[0107] As shown in the above results, the laminate of the present invention has water repellency and antiglare properties while having a certain light transmittance. That is, even when it is attached to the surface of a window, a solar panel, etc., it does not impair the visibility outdoors from the window or the power generation function of the solar panel, prevents the adhesion of icing, snowing, dirt, etc., and can further suppress the glare caused by light reflection.

[0108] The above-described embodiments are examples of the present invention, and the present invention is not limited to these examples. Well-known techniques, conventional techniques, and known techniques may be combined with or partially replaced in these examples. Also, modified inventions that can be easily conceived by those skilled in the art are included in the present invention.

Explanation of Reference Numerals

[0109] 10 Laminate 11 Base material 12 Filled particle-containing resin layer 12a Coating resin 12b Filled particles 13 Functional layer 13a Hydrophobic oxide fine particles

Claims

1. On a substrate, a resin layer containing filled particles and a functional layer are provided in this order, The resin layer containing filled particles contains filled particles having an average particle diameter of 3 μm or more and 200 μm or less in a coating resin, The functional layer is composed of hydrophobic oxide fine particles having an average primary particle diameter of 3 nm or more and 100 nm or less, and the stacking amount of the hydrophobic oxide fine particles is 0.3 g / m ２ or more and 20.0 g / m ２ or less. The laminate is characterized by this.

2. The laminate according to claim 1, wherein the light transmittance at a wavelength of 555 nm is 70% or more.

3. The laminate according to claim 1, wherein the 60-degree gloss value is 50 or less.

4. The laminate according to claim 1, wherein the occupancy ratio of the filled particles is 0.05 or more and 0.90 or less in the projected area in the plan view on the side where the functional layer of the resin layer containing filled particles is laminated.

5. The weight per unit area of the resin layer containing the filled particles is 1 g / m ２ or more and 200 g / m ２ or less. The laminate according to claim 1.

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