Laminate

Abstract

[Problem] To provide a laminate that is capable of maintaining good water repellency or oil repellency even after a long period of contact with oil or water. [Solution] A laminate comprising a base material and a functional layer, said laminate being characterized in that (1) the functional layer includes a three-dimensional network structure, and (2) the three-dimensional network structure includes (a) at least one type of functional particles from among (a1) composite particles that have a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) hydrophobic particles, and (b) a hydrophobic resin containing fluorine.

Description

Laminate

[0001] The present invention relates to a novel laminate, more specifically to a laminate having water-repellent and oil-repellent properties.

[0002] Water-repellent or oil-repellent technology has been widely studied for adhesion prevention, mold release, etc. In particular, for food, beverages, medicines, cosmetics, etc., products have been developed that have been treated with a super water-repellent finish that shows a contact angle with water of 150° or more, or a super oil-repellent finish that shows a contact angle with oil of 150° or more, with the aim of preventing or suppressing adhesion of the contents to the packaging material.

[0003] For example, a laminate is known in which a substrate film is provided with a porous functional layer containing a three-dimensional network structure formed by water- and / or oil-repellent fine particles adhering to one another and a thermoplastic resin, wherein the porous functional layer has a porosity of 1% by volume or more and 50% by volume or less in the thickness direction in a region from the bottom surface of the porous functional layer to 50% of the thickness, and a porosity of 50% by volume or more and 99% by volume or less in a region from the bottom surface of the porous functional layer to more than 50% of the thickness to the surface of the porous functional layer (Patent Document 1).

[0004] Japanese Patent Application Laid-Open No. 2021-146651

[0005] In the above-described conventional techniques, the three-dimensional mesh structure has a predetermined porosity, so that the fine particles are less likely to fall off and high water- and oil-repellency can be exhibited. However, when the three-dimensional mesh structure is used in contact with oil or water for a long period of time, the three-dimensional mesh structure may become immersed in oil, resulting in a decrease in water- or oil-repellency.

[0006] Therefore, a main object of the present invention is to provide a laminate that can maintain good water or oil repellency.

[0007] The present inventors have conducted extensive research in light of the problems of the prior art and have found that a laminate having a specific composition and structure can achieve the above object, thereby completing the present invention.

[0008] That is, the present invention relates to the following laminates. 1. A laminate comprising a substrate and a functional layer, wherein (1) the functional layer comprises a three-dimensional network structure, and (2) the three-dimensional network structure comprises (a) at least one type of functional particles selected from (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) hydrophobic particles, and (b) a fluorine-containing hydrophobic resin. 2. The laminate according to item 1 above, in which the functional particles are fixed to the three-dimensional network structure by the fluorine-containing hydrophobic resin. 3. The laminate according to item 1 above, in which the fluorine-containing hydrophobic resin adheres to the substrate and the functional particles, thereby supporting the functional layer on the substrate. 4. The laminate according to item 1 above, in which the specific surface area of ​​the functional layer is 2 to 195 m ２ / g. 5. The laminate according to item 1, wherein the porosity of a region of the functional layer from the bottom surface to 50% of the thickness is 0 to 45%, and the porosity of a region from the bottom surface to more than 50% of the thickness to the surface (outermost surface) of the functional layer is 10 to 55%. 6. The laminate according to item 1, wherein the ratio of the functional particles to the fluorine-containing hydrophobic resin (excluding the fluorine-containing hydrophobic resin contained in the functional particles) is 1:50 to 20:1 in terms of solids weight ratio. 7. The laminate according to item 1, wherein the fluorine-containing hydrophobic resin is at least one selected from the group consisting of polyfluoroalkyl methacrylate resin, polytetrafluoroethylene, and ethylene tetrafluoroethylene. 8. The laminate according to item 1, wherein the substrate is at least one selected from the group consisting of metal foil, metal plate, resin film, resin plate, paper, wood plate, nonwoven fabric, or primer-coated versions of these. 9. Item 1. A laminate according to item 1, wherein the inorganic oxide fine particles have an average primary particle diameter of 5 to 50 nm. 9. A laminate according to item 1, wherein the three-dimensional network structure further comprises filler particles having an average particle diameter D50 of 5 to 60 μm. 11. A method for producing a laminate comprising a substrate and a functional layer, comprising: (1) applying a fluorine-containing coating liquid containing a fluorine-containing hydrophobic resin to the substrate to form a fluorine-containing coating film; and (2) applying a coating liquid containing at least one type of functional particle selected from the group consisting of (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) hydrophobic particles to form a composite particle-containing coating film.

[0009] According to the present invention, it is possible to provide a laminate that can maintain good water repellency and / or oil repellency, i.e., a laminate that is more excellent in durability of water repellency and / or oil repellency (oil repellency durability, etc.).

[0010] In particular, the laminate of the present invention includes (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles, (a2) at least one type of functional particle, which is a hydrophobic particle, and (b) a three-dimensional network structure containing a fluorine-containing hydrophobic resin. Therefore, in addition to the high water and oil repellency due to the two components of the functional particles and the hydrophobic resin, the functional particles are relatively firmly fixed to the three-dimensional network structure and the substrate, which suppresses or prevents the functional particles from falling off over time, thereby imparting high durability to the water and / or oil repellency. Therefore, even when in contact with oil or moisture for a long period of time, high water and / or oil repellency can be exhibited. In particular, even when the functional layer is immersed in oil (e.g., oil at a high temperature of 50°C or higher), good water and / or oil repellency can be obtained, and the effect can be maintained for a relatively long period of time.

[0011] 4A is a schematic diagram showing an example of the layer structure of a laminate of the present invention. FIG. 4B is a cross-sectional image of a laminate of Comparative Example 1. FIG. 4C is a binarized image of Example 1. FIG. 4A shows a cross-sectional image of a laminate taken by an electron microscope as a secondary electron image. FIG. 4B shows a binarized image of FIG. 4A. FIG. 4C shows the results of performing a discriminant analysis method on FIG. 4A after selecting a bright area as an extraction area using an automatic binarization system.

[0012] 1. Laminate of the Present Invention The laminate of the present invention is a laminate comprising a substrate and a functional layer, characterized in that (1) the functional layer comprises a three-dimensional network structure, and (2) the three-dimensional network structure comprises (a) at least one type of functional particle selected from (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) hydrophobic particles, and (b) a fluorine-containing hydrophobic resin.

[0013] An example of an embodiment of the laminate of the present invention is shown in Fig. 1. In the laminate 10 of Fig. 1, a functional layer 12 is formed directly on a substrate 11. As shown in Fig. 1, the functional layer 12 includes a three-dimensional mesh structure 12a. As shown in Fig. 1, the functional layer 12 may include voids 12b.

[0014] The three-dimensional network structure 12a in FIG. 1 includes at least one type of functional particle A, which is (a1) a composite particle having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles, and (a2) a hydrophobic particle, and a fluorine-containing hydrophobic resin (hereinafter abbreviated as "fluorine-containing resin") B. In other words, the three-dimensional network structure is formed by bonding multiple functional particles together in a manner that bridges them with the fluorine-containing resin. In this way, the functional particles are fixed to the three-dimensional network structure by the fluorine-containing resin. As a result, the functional particle A is fixed to the functional layer 12, and the functional layer 12 is fixed to the substrate 11. In other words, the fluorine-containing resin adheres to the substrate 11 and the functional particle A, thereby supporting the functional layer 12 on the substrate. In this case, even if hydrophobic particles are used as functional particles, a three-dimensional network structure can be formed by similarly bonding multiple hydrophobic particles together in a manner that bridges them with the fluorine-containing resin, thereby achieving high water repellency and durability.

[0015] As shown in Fig. 1, a plurality of functional particles A (particle groups) are configured in a state of agglomeration with each other mainly via a fluorine-containing resin. In this case, the fluorine-containing resin is interposed between the plurality of functional particles A, but voids 12b may be present between the functional particles as long as the effects of the present invention are not impaired. Furthermore, although the functional particles A are usually indirectly in contact with each other via a fluorine-containing resin B, the functional particles may be in direct contact with each other as long as the effects of the present invention are not impaired.

[0016] For example, the structure of Comparative Example 1 is shown in Figure 3, and a three-dimensional network structure composed of functional particles is formed. That is, the functional particles (composite particles) are bonded together mainly by intermolecular forces to form a three-dimensional network structure (the fluororesin on the surfaces of adjacent functional particles is in contact with each other but is not bonded (fixed) as if bridged). In contrast, as shown in Figure 2 showing Example 1, the three-dimensional network structure is formed by the functional particles (composite particles) being bonded (fixed) as if bridged by the fluororesin. In this respect, the three-dimensional network structure of the present invention is distinguishable from a three-dimensional network structure composed essentially of functional particles only. Each component of the laminate of the present invention will be described in detail below.

[0017] (1) Substrate The substrate mainly functions as a support layer that supports the functional layer. Therefore, as long as it has such a function, the material thereof is not particularly limited, and examples thereof include metal foil (e.g., aluminum foil, etc.), metal plate (e.g., steel plate, etc.), resin film (e.g., synthetic resin such as polyester, polyethylene, polypropylene, etc.), resin plate (e.g., synthetic resin such as polyester, polyethylene, polypropylene, etc.), paper, wood board, nonwoven fabric, and primer-coated versions of these.

[0018] In particular, in the present invention, at least one resin film selected from the group consisting of polypropylene film, polyethylene film and polyester film, or metal foil (particularly aluminum foil) can be suitably used as the substrate.

[0019] When the substrate is a resin film, the resin film may be either a stretched film or an unstretched film. Furthermore, the stretched film may be either a uniaxially stretched film or a biaxially stretched film. Furthermore, various types of resin films that have been subjected to surface treatments such as corona treatment may also be used as the substrate.

[0020] The thickness of the substrate is not limited, but can be appropriately set depending on, for example, the material of the substrate, the use of the laminate of the present invention, etc. When the substrate is in the form of a film or the like, the thickness can generally be appropriately set within the range of about 20 to 80 μm, but is not limited thereto.

[0021] The substrate may be subjected to a surface treatment on its surface (particularly the surface on which the functional layer is laminated). This can further enhance the adhesion (adhesion) between the substrate and the functional layer. Examples of the surface treatment include unevenness treatment using an additive (preferably filler particles) and unevenness treatment by embossing. The height of the unevenness is not particularly limited, but is preferably about 5 to 60 μm, and more preferably 20 to 50 μm. Here, the filler particles may be those described below.

[0022] (2) Functional Layer The functional layer is a layer having water repellency and / or oil repellency and is formed on at least one surface of the substrate.

[0023] The functional layer has a three-dimensional network structure containing at least one functional particle selected from the group consisting of (a) (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) hydrophobic particles, and (b) a fluorine-containing hydrophobic resin. This structure provides water-repellent or oil-repellent properties, preventing or suppressing adhesion of objects to the functional layer.

[0024] The functional layer has a three-dimensional network structure and can be porous, so it has a predetermined specific surface area. In this case, the specific surface area is not limited, but is usually 2 to 195 m ２ Therefore, for example, 2 to 55 m ２ / g. This can also be an index of the degree of bridging between the fluorine-containing resin and the functional particles in the three-dimensional network structure of the functional layer. Note that the specific surface area in the present invention refers to the specific surface area measured by the BET method (Brunauer-Emmett-Teller method).

[0025] The relationship between the structure of the functional layer and the specific surface area will be explained below using specific numerical values ​​as an example for ease of understanding. The specific surface area of ​​the functional layer is maximum when only functional particles are applied to the substrate. For example, when the specific surface area is measured after only functional particles are applied to the substrate, it is approximately 200 m ２ / g. This is because the functional particles form a three-dimensional network structure solely through intermolecular forces, and when the porosity is measured using the method of Test Example 3 described later, it is approximately 55%, which is the theoretically highest level of voids in the functional layer. Since a functional layer consisting only of functional particles forms a three-dimensional network structure solely through intermolecular forces, there is a risk that the functional particles may easily fall off. The critical point is when the specific surface area is 195 m ２ / g, which exceeds this at 197m ２ At about 1 / g, the amount of fluorine-containing resin is insufficient, increasing the possibility that the functional particles will fall off.

[0026] Furthermore, when the functional layer is made of only a fluorine-containing resin and no functional particles are present, the surface becomes smooth and the specific surface area becomes the minimum. For example, even if only a polyfluoroalkyl methacrylate resin is applied to the substrate, the porosity is 0% and the specific surface area becomes the minimum of 0.2 m. ２ In this case, the three-dimensional network structure is almost completely lost, resulting in a functional layer with less air in the surface layer, and there is a risk that sufficient oil repellency durability will not be obtained. ２ / g, which is lower than 1m ２ At about 1 / g, there are almost no voids, and oil repellency or water repellency may be poor.

[0027] From the above, it can be said that there is a certain correlation between the porosity and specific surface area of ​​the functional layer. In theory, voids (i.e., air layers) are said to be the most repellent to substances, with a contact angle of 180° for water or oil. According to the Cassie-Baxter theory, this mosaic structure of air layers and solid substances is said to depend on the proportion of air layers and the liquid-repellent ability of the solid substance itself.

[0028] As mentioned above, even if the porosity is maximized, if the functional particles are formed only by intermolecular forces, the functional particles will easily fall off, and therefore the material that holds the three-dimensional knitted structure is important. Therefore, in the present invention, a hydrophobic resin containing fluorine is used to support the functional particles. If a material other than the above-mentioned fluorine-containing resin is used as the resin that bridges the functional particles, sufficient oil repellency or water repellency cannot be obtained. This is because the surface free energy (surface tension of a solid) of a material containing fluorine is generally 20 mJ / m ２ For example, the surface tension of the edible oil used in Test Example 5 described later is 32 mJ / m ２ On the other hand, the surface free energy of fluorine-free resins such as olefin and styrene-butadiene rubber is 30 to 34 mJ / m ２ The surface tension of cooking oil is about 32 mJ / m ２ Therefore, it is thought that the surface becomes easily wetted with oil, resulting in a decrease in oil repellency or water repellency. In this respect, the surface free energy of the fluorine-containing resin used in the present invention is usually 5 to 25 mJ / m ２ It is sufficient to set the intensity to about 5 to 20 mJ / m ２ It is more preferable to set the following.

[0029] Considering oil-repellent or water-repellent durability, it is desirable to bridge and reinforce the functional particles with a fluorine-containing resin while maintaining a predetermined void space. Furthermore, if a fluorine-containing hydrophobic resin is not used as such a resin, it becomes difficult to fully exhibit oil-repellent or water-repellent properties. The larger the void space, the better from the viewpoint of oil-repellent or water-repellent properties. However, if the void space is too large, the physical structure tends to become brittle. In this case, the bottom is filled with the fluorine-containing resin, and even if the void space is 0%, the oil-repellent or water-repellent properties are maintained as long as the void space at the top is 10% or more.

[0030] On the other hand, if the porosity of the bottom is 0% and the porosity of the top is 2%, there are too few voids and sufficient oil or water repellency may not be obtained. If the porosity of the bottom is 0% but the porosity of the top is 10%, the desired oil or water repellency can be maintained, although the effect is not as great.

[0031] Here, the "bottom" refers to the region of the functional layer from the bottom surface of the functional layer on the substrate side to 50% of the thickness, as shown in Fig. 1. The "upper" refers to the region of the functional layer from the bottom surface of the functional layer to more than 50% of the thickness to the surface (outermost surface) of the functional layer, as shown in Fig. 1.

[0032] On the other hand, when only functional particles are applied, the porosity reaches its maximum at 55% at the bottom and 55% at the top. As mentioned above, since the functional particles are essentially bonded solely by intermolecular forces, they may easily fall off. A porosity of 45% at the bottom and 55% at the top is the critical point, where oil-repellent or water-repellent durability can be maintained, although not sufficiently. At porosities above this level, it is presumed that the bridging effect of the fluorine-containing resin is insufficient, and oil-repellent or water-repellent durability may not be maintained at a porosity of 53% at the bottom and 55% at the top. From this perspective, the porosity can be in the range of approximately 0-45% at the bottom and approximately 10-55% at the top, but a porosity of 31-45% at the bottom and 40-55% at the top is particularly preferred, with a porosity of 35-41% at the bottom and 44-48% at the top being even more preferred. In particular, it is preferable for the functional layer to have a gradient structure in which the porosity increases from the bottom to the top. Therefore, it is desirable that the porosity of the top portion is greater than that of the bottom portion. For example, the difference between the two [(top porosity) - (bottom porosity)] is preferably 3% or more, and more preferably 4 to 15%.

[0033] The ratio of functional particles to fluorine-containing resin (excluding the fluorine-containing hydrophobic resin contained in the functional particles) in the three-dimensional network structure is typically about 1:50 to 20:1 by solid weight, preferably 1:30 to 20:1, more preferably 1:10 to 4:1, and most preferably 1:3 to 4:1. By setting the ratio within this range, a three-dimensional network structure is formed in which the functional particles are firmly bridged by the fluorine-containing hydrophobic resin. In this case, if the ratio of fluorine-containing resin increases and exceeds 1:30, the fluorine-containing resin bridging the functional particles will completely fill the gaps between the functional particles, making it impossible to maintain the three-dimensional network structure. This results in properties equivalent to those obtained when only fluorine-containing resin is applied to the substrate, and sufficient oil repellency or water repellency cannot be obtained. This means that the specific surface area approaches the value when a fluorine-containing resin coating is applied to the substrate. On the other hand, if the ratio of functional particles is greater than 20:1 and there is an excessive amount of functional particles, the coating film will be closer to being made up of functional particles only, and the fluorine-containing resin will not be able to bridge the functional particles together, so sufficient adhesion will not be obtained and it is thought that oil repellency durability or water repellency durability will not be exhibited.

[0034] (2-1) Hydrophobic Particles As the hydrophobic particles, at least one type of inorganic oxide particles (powder) such as silicon oxide, titanium oxide, aluminum oxide, zinc oxide, etc. Among these, silicon oxide particles are more preferred.

[0035] Furthermore, hydrophobic particles that can be used include hydrophilic particles that have been hydrophilized by etching, ultraviolet irradiation, blasting, plasma treatment, etc., and then hydrophobized with a silane coupling agent, etc., leaving hydroxyl groups partially intact. These particles form a functional layer with a three-dimensional network structure, which allows the surface on the primer layer side to strongly bond to the thermosetting resin, and the other surface to exhibit super-water repellency and / or super-oil repellency.

[0036] The inorganic oxide particles preferably have an average primary particle diameter of 5 to 50 nm, and particularly desirably 7 to 30 nm. The average primary particle diameter of the inorganic oxide particles can be measured using a transmission electron microscope or a scanning electron microscope. More specifically, the average primary particle diameter can be determined by taking a photograph using a transmission electron microscope or a scanning electron microscope, measuring the diameters of 200 or more particles on the photograph, and calculating the arithmetic mean value.

[0037] The nano-level inorganic oxide particles are not limited, and known or commercially available ones can be used. For example, silica products include those with the product names "AEROSIL R972," "AEROSIL R972V," "AEROSIL R972CF," "AEROSIL R974," "AEROSIL RX200," and "AEROSIL RY200" (all manufactured by Nippon Aerosil Co., Ltd.), "AEROSIL R202," "AEROSIL R805," "AEROSIL R812," and "AEROSIL R812S" (all manufactured by Evonik Degussa), and "Sylohobic 100," "Sylohobic 200," and "Sylohobic 603" (all manufactured by Fuji Silysia Chemical Ltd.). Titania products include those with the product names "AEROXIDE TiO ２ Examples of alumina include "AEROXIDE Alu C" (manufactured by Evonik Degussa) and other fine particles whose particle surfaces have been made hydrophobic by treating them with a silane coupling agent.

[0038] Among these, hydrophobic silica fine particles are preferably used. In particular, hydrophobic silica fine particles having trimethylsilyl groups on the surface are preferred in that they provide superior non-adhesive properties. Commercially available products corresponding to these fine particles include the aforementioned "AEROSIL R812" and "AEROSIL R812S" (both manufactured by Evonik Degussa).

[0039] The amount of hydrophobic particles attached (weight after drying) is not limited, but is usually 0.01 to 100 g / m ２ The thickness can be set within a range of about 0.01 to 50 g / m ２It is more preferable to set the density to 0.1 to 50 g / m ２ It is more preferable to set the density to 2 to 10 g / m ２ It is most preferable to set the following.

[0040] (2-1) Composite particles Composite particles are characterized by having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles. That is, they are particles in which inorganic oxide fine particles are used as core particles and a coating layer containing a polyfluoroalkyl methacrylate resin is formed on the surface of the core particles.

[0041] The inorganic oxide fine particles that become the core particles are not particularly limited, but for example, at least one kind of particles (powder) of silicon oxide, titanium oxide, aluminum oxide, zinc oxide, etc. Among these, silicon oxide particles are preferred.

[0042] The size of the inorganic oxide microparticles is not limited, but the average primary particle diameter is usually preferably about 5 to 50 nm, and more preferably 7 to 30 nm. The average primary particle diameter can be measured using a transmission electron microscope or a scanning electron microscope. More specifically, the average primary particle diameter can be determined by taking a photograph with a transmission electron microscope or a scanning electron microscope, measuring the diameters of 200 or more particles on the photograph, and calculating the arithmetic mean value.

[0043] As the nano-level inorganic oxide fine particles, known or commercially available ones can be used. Examples of silicon oxide include products with the product names "AEROSIL 200" ("AEROSIL" is a registered trademark, the same applies hereinafter), "AEROSIL 130", "AEROSIL 300", "AEROSIL 50", "AEROSIL 200FAD", and "AEROSIL 380" (all manufactured by Nippon Aerosil Co., Ltd.). Examples of titanium oxide include products with the product name "AEROXIDE TiO ２ Examples of aluminum oxide include "AEROXIDE Alu C 805" (manufactured by Evonik Degussa).

[0044] The method for preparing the composite particles is not particularly limited, and for example, a polyfluoroalkyl methacrylate resin may be used as a coating material for inorganic oxide fine particles (powder), and a coating layer may be formed according to a known coating method, granulation method, etc. More specifically, the composite particles can be suitably prepared by a production method including a step (coating step) of coating inorganic oxide fine particles with a coating liquid prepared by dissolving or dispersing a liquid polyfluoroalkyl methacrylate resin in a solvent.

[0045] As such a resin, known or commercially available resins can be used. Commercially available products include, for example, the product name "CHEMINOX FAMAC-6" (manufactured by Unimatec (Japan)), the product name "Zonyl TH Fluoromonomer code 421480" (manufactured by SIGMA-ALDRICH (USA)), the product name "SCFC-65530-66-7" (manufactured by Maya High Purity Chem (CHINA)), the product name "FC07-04 to 10" (Fluory, Inc (USA)), the product name "CBINDEX: 58" (manufactured by Wilshire Chemical Co., Inc (USA)), the product names "Asahiguard AG-E530" and "Asahiguard AG-E060" (both manufactured by Asahi Glass Co., Ltd.), and the product name "TEMAc-N" (Top Examples of suitable fluororesin include those under the product name "Zonyl 7950" (manufactured by SIGMA-RBI (SWITZ)), those under the product name "6100840 to 6100842" (manufactured by Weibo Chemical Co., Ltd. (CHINA)), and those under the product name "CB INDEX: 75" (manufactured by ABCR GmbH & Co. KG (Germany)).

[0046] In the above-described manufacturing method, a polyfluoroalkyl methacrylate resin that is liquid at room temperature (25°C) and under normal pressure can be suitably used. As such a polyfluoroalkyl methacrylate resin, commercially available products such as those listed above can also be used. Among these, a copolymer of a) polyfluorooctyl methacrylate, b) 2-N,N-diethylaminoethyl methacrylate, c) 2-hydroxyethyl methacrylate, and d) 2,2'-ethylenedioxydiethyl dimethacrylate can be suitably used as the resin, in view of the ability to achieve superior water repellency and oil repellency. These can also be commercially available products.

[0047] The solvent used in the coating liquid is not particularly limited, and in addition to water, organic solvents such as alcohol and toluene can be used, but in the present invention, it is preferable to use water. That is, it is preferable to use a coating liquid in which the polyfluoroalkyl methacrylate resin is dissolved and / or dispersed in water.

[0048] The content of the polyfluoroalkyl methacrylate resin in the coating liquid is not particularly limited, but is generally about 10 to 80% by weight, preferably 15 to 70% by weight, and more preferably within the range of 20 to 60% by weight.

[0049] The method for coating the surface of the inorganic oxide fine particles with the coating liquid may be any known method, such as a spraying method, a dipping method, a stirring granulation method, etc. In particular, in the present invention, coating by a spraying method is particularly preferred because it is excellent in uniformity, etc.

[0050] After coating with the coating liquid, composite particles can be obtained by removing the solvent through heat treatment. The heat treatment temperature is usually about 150 to 250°C, and preferably 180 to 200°C. The heat treatment atmosphere is not limited, but an inert gas (non-oxidizing) atmosphere such as nitrogen gas or argon gas is preferable. Furthermore, for example, if necessary, a series of steps consisting of the coating step and the heat treatment step can be performed one or more times. This allows for the appropriate control of the coating amount, etc.

[0051] The surfaces of the composite particles thus obtained have a coating layer containing a polyfluoroalkyl methacrylate resin, which has excellent affinity with inorganic oxide fine particles and allows a relatively strong coating layer with high adhesion to be formed on the particle surface, while also allowing for higher water repellency or oil repellency to be achieved.

[0052] The amount of composite particles attached (weight after drying) may be an amount sufficient to form a three-dimensional network structure, but is usually 0.01 to 100 g / m ２ The thickness may be within a range of about 0.1 to 20 g / m ２ It is preferable that the density is about 0.5 to 10 g / m ２ It is more preferable to set the density to 0.6 to 5 g / m ２ It is most preferable to do so.

[0053] (2-2) Fluorine-Containing Resin The fluorine-containing resin constitutes a three-dimensional network structure together with the functional particles in the functional layer. The fluorine-containing resin is itself hydrophobic or lipophobic, and therefore easily repels water or substances containing a large amount of water. The fluorine-containing resin also easily repels oil or substances containing a large amount of oil. Furthermore, in the present invention, the fluorine-containing resin bonds the functional particles together, thereby forming a three-dimensional network structure between the fluorine-containing resin and the functional particles. By adopting such a structure, the water repellency and oil repellency are further enhanced. Furthermore, it is preferable that the fluorine-containing resin bonds the substrate and the functional particles, thereby supporting (fixing) the functional particles to the substrate. This allows the functional layer to be more firmly fixed to the substrate, resulting in high durability.

[0054] The fluorine-containing resin is not limited as long as it contains fluorine and has hydrophobicity, and can be appropriately selected from synthetic resins obtained by polymerizing fluorine-containing monomers. These may be homopolymers or copolymers. For example, at least one of polyfluoroalkyl methacrylate resin, polytetrafluoroethylene resin (PTFE), ethylene tetrafluoroethylene resin (ETFE), polyvinylidene difluoride resin, ethylene-tetrafluoroethylene copolymer, perfluoroalkoxyalkane resin, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, etc. can be mentioned. The properties of these resins are not limited, and for example, aqueous dispersion type resins can be suitably used.

[0055] In particular, in the present invention, at least one selected from the group consisting of polyfluoroalkyl methacrylate resin, polytetrafluoroethylene resin (PTFE), ethylene tetrafluoroethylene resin (ETFE), perfluoroalkoxyalkane resin, and tetrafluoroethylene-hexafluoropropylene copolymer can be preferably used. These may be publicly known or commercially available products.

[0056] Among these, in the present invention, it is preferable that the fluorine-containing resin contains a polyfluoroalkyl methacrylate resin. In particular, when composite particles are used as functional particles, by incorporating a fluorine-containing resin that is substantially the same as the coating layer formed on the surface of the inorganic oxide fine particles into the functional layer, the affinity between the functional particles and the fluorine-containing resin is increased, and higher water repellency durability and oil repellency durability can be achieved. The same resins as those described above can be used, and commercially available products can also be used.

[0057] The amount of the fluorine-containing resin to be applied (weight after drying) may be an amount sufficient to form a three-dimensional network structure, but is usually 0.5 to 30 g / m ２ It is preferable to set the density to 0.5 to 5 g / m ２ It is more preferable to set the density to 2.5 to 5 g / m ２It is most preferable to do so.

[0058] Furthermore, the ratio (weight ratio) of the functional particles (A) to the fluorine-containing resin (excluding the fluorine-containing hydrophobic resin contained in the functional particles) (B) in the three-dimensional network structure can be set, for example, to about A:B=20:1 to 1:50, as described above, or about A:B=20:1 to 1:30, but is not limited thereto. Therefore, for example, the weight ratio of functional particles (A) to fluorine-containing resin (B) can be set to about A:B=1:0.5 to 1:3.

[0059] (2-4) Other Components In the present invention, other components may be contained in the functional layer (or the three-dimensional network structure) within a range that does not impair the effects of the present invention. Examples of such additives include filler particles, colorants, dispersants, anti-settling agents, and anti-foaming agents. The total content of the additives in the functional layer can be, for example, about 50% by weight or less, and can be, for example, about 0 to 40% by weight, but is not limited thereto.

[0060] In particular, filler particles can be preferably used in the present invention. The inclusion of filler particles in combination with inorganic oxide fine particles can form a nano-microstructure, thereby exhibiting higher water repellency or oil repellency. Filler particles having an average particle diameter D50 of 5 to 60 μm (preferably 10 to 30 μm) can be preferably used. The material may be either an inorganic or organic material, such as at least one particle (powder) selected from the group consisting of polymethyl methacrylate (PMMA), styrene, low-density polyethylene (LDPE), high-density polyethylene (HDPE), acrylic resin, silica, and alumina. When filler particles are incorporated, their content is not limited, but it is preferable that the filler particles are included in a proportion such that the ratio of [fluorine-containing resin / (filler particles + fluorine-containing resin)] after drying is 25 to 75 wt %. If this proportion is less than 25 wt %, the fluorine-containing resin may not be able to sufficiently bond the filler particles to the substrate, making the filler particles more likely to fall off. Even if the proportion exceeds 75% by weight, for example, the fluorine-containing resin is 100% by weight with no filler particles present, it is possible to obtain the desired oil repellency or water repellency durability.

[0061] 2. Method for Producing Laminate The laminate of the present invention can be suitably produced, for example, by the following first to third methods.

[0062] The first method is a manufacturing method including (1) a step of forming a coating film by applying to a substrate a coating liquid containing (a) (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles, (a2) at least one type of functional particles selected from hydrophobic particles, and (b) a fluorine-containing resin (coating film forming step), and, if necessary, (2) a step of heat-treating the coating film (heat treatment step).

[0063] The second method is a production method including: (1) a step of forming a fluorine-containing coating film by applying a fluorine-containing coating liquid containing a fluorine-containing resin to a substrate (fluorine-containing coating film forming step); (2) a step of forming a functional particle-containing coating film by applying a coating liquid containing at least one type of functional particle selected from (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) hydrophobic particles to the surface of the fluorine-containing coating film (composite particle-containing coating film forming step); and, if necessary, (3) a step of heat-treating the coating film obtained by the above step (heat treatment step).

[0064] The third method is a production method including: (1) a step of forming a functional particle-containing coating film by applying to a substrate a coating liquid containing at least one type of functional particles selected from (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) hydrophobic particles (composite particle-containing coating film forming step); (2) a step of forming a fluorine-containing coating film by applying a fluorine-containing coating liquid containing a fluorine-containing resin to the functional particle-containing coating film (fluorine-containing coating film forming step); and, if necessary, (3) a step of heat-treating the coating film obtained by the above step (heat treatment step).

[0065] Among these, the second method can be more preferably adopted. This allows the construction and reinforcement of a three-dimensional network structure while more reliably maintaining voids (i.e., maintaining high oil repellency). The reason for this is unclear, but it is presumed that the functional particles arranged on the fluorine-containing coating film absorb the fluorine-containing resin by capillary action and act as a bridge. This makes it possible to more effectively suppress or prevent the functional particles from falling off, resulting in excellent water-repellent or oil-repellent durability.

[0066] <Regarding the first method> Coating film formation step In the coating film formation step, a coating film is formed by applying to a substrate a coating liquid containing (a) (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) at least one type of functional particles selected from hydrophobic particles, and (b) a fluorine-containing resin.

[0067] The coating liquid usually contains functional particles, a fluorine-containing resin, and a solvent. The types of functional particles and fluorine-containing resin, the ratio of the two, etc. may be within the ranges described above.

[0068] The solvent is not limited and can be appropriately selected depending on the type of fluorine-containing resin used, etc. For example, the solvent can be appropriately selected from organic solvents such as alcohol-based solvents (ethanol, methanol, isopropyl alcohol (IPA), hexyl alcohol, etc.), ketone-based solvents (acetone, ketone, methyl ethyl ketone (MEK), etc.), hydrocarbon-based solvents (cyclohexane, normal pentane, normal hexane methyl cyclohexane (MCH), etc.), aromatic solvents (toluene, etc.), and glycol-based solvents (propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol, etc.).

[0069] The coating liquid may be a solution in which a fluorine-containing resin or the like is dissolved in a solvent, but it is particularly desirable that the coating liquid be in the form of a dispersion in which functional particles and fluorine-containing resin particles are dispersed in a solvent. This allows the functional particles and fluorine-containing resin particles to be uniformly coated when the coating liquid is applied to a substrate, thereby maintaining the properties of the functional particles and improving adhesion between the functional particles as well as adhesion between the functional layer and the substrate. When such a dispersion is applied to a substrate, many of the functional particles and fluorine-containing resin particles move downward (in the direction of gravity), resulting in a low porosity in the region of the functional layer close to the substrate and a high porosity in the region on the outermost surface of the functional layer. In this way, a functional layer with a gradient structure can be effectively formed.

[0070] The method for applying the coating liquid is not particularly limited, and known methods such as roll coating, various gravure coatings, bar coater, doctor blade coating, comma coater, spray coating, and brush coating can be appropriately used.

[0071] After application, a drying step may be carried out as necessary. The drying method is not particularly limited, and may be either natural drying or heat drying. When heat drying is performed, the heating temperature is not limited, but is usually about 80 to 140°C, and in particular 100 to 120°C. The heating time may be set appropriately depending on the heating temperature, etc., and is usually about 3 to 60 seconds, but is not limited thereto.

[0072] Heat Treatment Step In the present invention, if necessary, the coating film obtained in the coating film formation step can be heat-treated in the heat treatment step. By heat treatment, the functional particles and the fluorine-containing resin in the functional layer are more firmly bonded, and the fluorine-containing resin is also bonded to the substrate, thereby obtaining a laminate with better adhesion between the substrate and the functional layer. Furthermore, in the heat treatment step, part of the functional particles and / or the fluorine-containing resin can be embedded in the substrate, thereby obtaining higher adhesion and more effectively forming an integral structure between the substrate and the functional layer.

[0073] The heat treatment temperature is preferably set to a temperature lower than the heat resistance temperature of the substrate and in a temperature range from the lowest glass transition temperature to the melting point of the fluorine-containing resin contained in the functional layer. Therefore, for example, if the heat resistance temperature of the substrate is 660°C and the fluorine-containing resin has a glass transition temperature of 100°C and a melting point of 270°C, the heat treatment temperature can be set to about 100 to 270°C (or, for example, about 150 to 200°C).

[0074] The heat treatment time may be set to a time sufficient to obtain the desired adhesion, and may be set to, for example, about 10 seconds to 60 minutes, but is not limited to this.

[0075] <Second Method> Fluorine-containing coating film forming step In the fluorine-containing coating film forming step, a fluorine-containing coating liquid containing a fluorine-containing resin is applied to a substrate to form a fluorine-containing coating film.

[0076] The coating liquid usually contains a fluorine-containing resin and a solvent. The type of fluorine-containing resin, the ratio of the two, and the like can be set as described above. The solvent can be the same as that described in the first method.

[0077] The coating liquid may be a solution in which the fluorine-containing resin is dissolved in a solvent, but is preferably in the form of a dispersion in which fluorine-containing resin particles are dispersed in a solvent. This allows the fluorine-containing resin particles to be uniformly coated when the coating liquid is applied to the base film, thereby further improving the adhesion between the functional layer to be finally formed and the substrate.

[0078] The coating method is not particularly limited, and known methods such as roll coating, various gravure coatings, bar coater, doctor blade coating, comma coater, spray coating, brush coating, etc. may be appropriately used. The coating amount is 0.1 to 60 g / m2 in terms of weight after drying. ２ The thickness can be about 0.2 to 50 g / m ２ However, the present invention is not limited to these.

[0079] After application, a drying step may be carried out as necessary. The drying method is not particularly limited, and may be either natural drying or heat drying. When heat drying is performed, the heating temperature is not particularly limited, but is usually about 80 to 140°C, and in particular 100 to 120°C. The heating time may be set appropriately depending on the heating temperature, etc., and is usually about 3 to 60 seconds, but is not limited to this.

[0080] Functional particle-containing coating film forming step In the functional particle-containing coating film forming step, a coating liquid containing at least one type of functional particles selected from (a) (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) hydrophobic particles is applied to the fluorine-containing coating film to form a functional particle-containing coating film.

[0081] The coating liquid usually contains functional particles and a solvent. The type of functional particles, the manufacturing method, etc. are as described above. The solvent, etc., may also be the same as those listed in the first method. The solid content concentration of the coating liquid may be, for example, within the range of about 20 to 60 wt %, but is not limited thereto.

[0082] The coating liquid is preferably in the form of a dispersion in which functional particles are dispersed in a solvent. This allows the functional particles to be uniformly coated when the coating liquid is applied to a fluorine-containing coating film, thereby further improving the adhesion between the finally formed functional layer and the substrate. Therefore, in this respect, when composite particles are used as the functional particles, it is preferable to use a solvent that does not dissolve the coating layer of the composite particles.

[0083] The method for applying the coating liquid is not particularly limited and may be carried out in the same manner as the method for forming a fluorine-containing coating film, for example, known methods such as roll coating, various gravure coatings, bar coater, doctor blade coating, comma coater, spray coating, brush coating, etc. may be appropriately adopted.

[0084] After application, a drying step may be carried out as necessary. The drying method is not particularly limited, and may be either natural drying or heat drying. When heat drying is performed, the heating temperature is not limited, but is usually about 80 to 140°C, and in particular 100 to 120°C. The heating time may be set appropriately depending on the heating temperature, etc., and is usually about 3 to 60 seconds, but is not limited thereto.

[0085] Heat Treatment Step In the present invention, if necessary, the coating film obtained in the coating film formation step (i.e., the coating film containing the fluorine-containing resin and functional particles) can be further heat-treated. By carrying out the heat treatment, the functional particles and the fluorine-containing resin in the porous functional layer are more firmly bonded, and the fluorine-containing resin is also bonded to the substrate, thereby obtaining a laminate with superior adhesion between the substrate and the porous functional layer. Furthermore, in the heat treatment step, part of the functional particles and / or the fluorine-containing resin can be embedded in the substrate, thereby obtaining higher adhesion and more effectively forming an integrated structure between the substrate and the functional layer.

[0086] The heat treatment temperature is preferably set to a temperature lower than the heat resistance temperature of the substrate and in a temperature range from the lowest glass transition temperature to the melting point of the fluorine-containing resin contained in the functional layer. Therefore, for example, if the heat resistance temperature of the substrate is 660°C, and the glass transition temperature and melting point of the fluorine-containing resin are 100°C and 270°C, respectively, the heat treatment temperature can be set to about 100 to 270°C (particularly about 150 to 220°C).

[0087] The heat treatment time may be set to a time sufficient to obtain the desired adhesion, and may be set to, for example, about 10 seconds to 60 minutes, but is not limited to this.

[0088] <Regarding the Third Method> The third method can be carried out in the same manner as the second method, except that the order of the fluorine-containing coating film forming step and the functional particle-containing coating film forming step of the second method is reversed.

[0089] 3. Use of the Laminate The laminate of the present invention can be used in a variety of applications requiring at least one of adhesion prevention, stain resistance, water repellency, oil repellency, and the like.

[0090] For example, it can be suitably used as a packaging material or container for packaging or sealing foods, medicines, cosmetics, etc. For example, various contents can be filled into a packaging bag formed using the laminate of the present invention with the functional layer facing inside, to provide a sealed packaged product.

[0091] The features of the present invention will be described in more detail below with reference to examples and comparative examples, but the scope of the present invention is not limited to these examples.

[0092] [Example 1] (1) Coating of Fluorine-Containing Resin A commercially available aluminum foil (manufactured by Toyo Aluminum K.K., 1N30, soft aluminum foil, thickness 30 μm) was used as a substrate. In addition, a fluorine-containing resin, polyfluoroalkyl methacrylate resin (PFMA) (manufactured by AGC, "AG-E060", surface free energy 14 mJ / m ２ To 100 parts by weight of a 20% by weight aqueous dispersion of 20% by weight of ethanol was added 100 parts by weight of ethanol, and the mixture was thoroughly stirred to prepare a coating liquid (dispersion). The coating liquid was applied to a coating solution of 5.0 g / m2 after drying using a bar coater #14. ２ After that, the coating was applied to the surface of the aluminum foil so that the coating was as follows: the coating was heated in an oven at 120°C for 40 seconds to evaporate the solvent, thereby forming a fluorine-containing coating film. (2) Formation of functional layer (2-1) Preparation of composite particles Hydrophilic silica particles (product name "AEROSIL 200", manufactured by Nippon Aerosil Co., Ltd., BET specific surface area 200 m) were used. ２100 g of a composite particle-containing dispersion (100 g of fluororesin (100 g / g, average primary particle diameter 12 nm) was placed in a reaction vessel, and 500 g of a commercially available surface treatment agent was sprayed onto the dispersion while stirring under a nitrogen gas atmosphere. The mixture was then stirred at 200°C for 30 minutes and then cooled. This yielded a powder composed of composite particles. The surface treatment agent used was a polyfluoroalkyl methacrylate resin (PFMA) consisting of an aqueous dispersion (solids concentration: 20% by mass) of a copolymer of polyfluorooctyl methacrylate, 2-N,N-diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, and 2,2'-ethylenedioxydiethyl dimethacrylate. (2-2) Preparation of Composite Particle-Containing Dispersion: A composite particle-containing dispersion was prepared by adding and mixing 50 parts by weight of the obtained composite particles with 50 parts by weight of ethanol. (2-3) Coating of Composite Particle-Containing Dispersion: The obtained composite particle-containing dispersion was applied to the fluorine-containing coating film using a #8 bar coater, and then dried at 120°C for 40 seconds to form a functional layer. The coating amount of the composite particles in the functional layer was determined by coating the composite particles in advance on another substrate under the same conditions with a bar coater, and drying the resultant composite particles to a weight of 2.0 g / m ２ It was confirmed in advance that the above conditions were met. In this way, a laminate having a functional layer formed on the surface of the substrate was produced. The production conditions, etc. in Example 1 are also shown in Table 1. The production conditions, etc. of the following Examples and Comparative Examples are also shown in Table 1.

[0093] [Example 2] When forming a fluorine-containing coating film, a polyfluoroalkyl methacrylate resin (AGC "AG-E060", surface free energy 14 mJ / m ２ A laminate having a functional layer formed on the surface of a substrate was produced in the same manner as in Example 1, except that 100 parts by weight of PTFE powder (aqueous dispersion type with a solid content of 20% by mass), 20 parts by weight of PTFE powder ("TLP10F-1" manufactured by Mitsui Chemours Fluoro Products Co., Ltd.), and 100 parts by weight of ethanol were placed in a mixer ("Awatori Rentaro ARV-310" manufactured by Thinky Corporation), and mixed for 1 minute 30 seconds at 2000 rpm to prepare a coating liquid, which was then applied using a #10 bar coater.

[0094] [Example 3] When forming a fluorine-containing coating film, a polyfluoroalkyl methacrylate resin ("AGE-060" manufactured by AGC, surface free energy 14 mJ / m ２ A laminate having a functional layer formed on the surface of a substrate was produced in the same manner as in Example 1, except that 100 parts by weight of filler particles (Mipelon (registered trademark) XM221U manufactured by Mitsui Chemicals, Inc., polyethylene beads (HDPE), average particle size 25 μm) were added to 100 parts by weight of a coating solution (aqueous dispersion type with a solid content of 20% by mass), 20 parts by weight of filler particles (Mipelon (registered trademark) XM221U manufactured by Mitsui Chemicals, Inc., polyethylene beads (HDPE), average particle size 25 μm), and 120 parts by weight of ethanol were added to a mixer (Thinky Corporation's Awatori Rentaro ARV-310), and the mixture was mixed for 1 minute 30 seconds at 2000 rpm to prepare a coating solution, which was then applied using a #10 bar coater.

[0095] [Example 4] When forming a fluorine-containing coating film, polytetrafluoroethylene ("TLP10F-1" manufactured by Mitsui Chemours Fluoroproducts Co., Ltd., surface free energy 5 mJ / m ２ A coating solution was prepared by adding 100 parts by weight of ethanol to 100 parts by weight of the composite particle-containing dispersion and thoroughly stirring the mixture. This coating solution was applied using a bar coater #14, and then a laminate having a functional layer formed on the surface of the substrate was produced in the same manner as in Example 1, except that the composite particle-containing dispersion was dried at 200°C for 60 minutes after application.

[0096] [Example 5] When forming a fluorine-containing coating film, a polyfluoroalkyl methacrylate resin (AGC "AG-E060", surface free energy 14 mJ / m ２ To 100 parts by weight of the acrylic resin (aqueous dispersion type with a solid content of 20% by mass), 200 parts by weight of ethanol was added, and the mixture was thoroughly stirred to prepare a coating liquid. This coating liquid was used to coat a acrylic resin with a coating weight of 0.5 g / m2 after drying using a bar coater #3. ２ A laminate having a functional layer formed on the surface of the substrate was produced in the same manner as in Example 1, except that the coating was performed so that the thickness of the functional layer formed on the surface of the substrate was 100 μm.

[0097] [Example 6] When forming a fluorine-containing coating film, a polyfluoroalkyl methacrylate resin (AGC "AG-E060", surface free energy 14 mJ / m ２(aqueous dispersion type with a solid content of 20% by mass) was dried with a bar coater #36 to a weight of 15 g / m ２ After coating so that the coating weight is 30 g / m, the coating is heated and dried in an oven at 120°C for 60 seconds to evaporate the solvent, and this process is repeated twice to obtain a total coating weight of 30 g / m ２ The composite particle-containing dispersion was then coated with a bar coater #5 until the coating amount of the composite particles was 1.0 g / m ２ A laminate having a functional layer formed on the surface of the substrate was produced in the same manner as in Example 1, except that the functional layer was formed by coating the substrate with the functional layer so that the coating would become

[0098] [Example 7] The composite particle-containing dispersion was applied using a bar coater #3, and the coating amount of the composite particles after drying was 0.5 g / m ２ A laminate having a functional layer formed on the surface of the substrate was produced in the same manner as in Example 1, except that:

[0099] [Example 8] The composite particle-containing dispersion was applied using a bar coater #14, and the coating amount of the composite particles after drying was 5.0 g / m ２ A laminate having a functional layer formed on the surface of the substrate was produced in the same manner as in Example 1, except that:

[0100] [Example 9] When forming a fluorine-containing coating film, a polyfluoroalkyl methacrylate resin (AGC "AG-E060", surface free energy 14 mJ / m ２ (aqueous dispersion type with a solid content of 20% by mass) was applied to a bar coater #8 to dry and then the weight was 2.5 g / m ２ Subsequently, the composite particle-containing dispersion was applied onto the fluorine-containing coating film using a bar coater #36, dried under conditions of 120°C x 60 seconds, and then again applied using a bar coater #36, dried under conditions of 120°C x 60 seconds, and then further applied using a bar coater #20, and dried under conditions of 120°C x 60 seconds, so that the coating amount of the composite particles after drying was 50 g / m ２A laminate having a functional layer formed on the surface of the substrate was produced in the same manner as in Example 1, except that:

[0101] [Example 10] When forming a fluorine-containing coating film, a polyfluoroalkyl methacrylate resin (AGC "AG-E060", surface free energy 14 mJ / m ２ 100 parts by weight of a water-based dispersion with a solid content of 20% by mass) was mixed with 180 parts by weight of filler particles (Technopolymer SBX-17 manufactured by Sekisui Plastics Co., Ltd., polystyrene beads, average particle size 17 μm) and 250 parts by weight of ethanol in a mixer (Thinky Corporation's Awatori Rentaro ARV-310), and the mixture was mixed for 1 minute 30 seconds at 2000 rpm to prepare a coating solution. The mixture was coated with a bar coater #3 and dried to a weight of 2.5 g / m. ２ A laminate having a functional layer formed on the surface of the substrate was produced in the same manner as in Example 1, except that the coating was performed so that the thickness of the functional layer formed on the surface of the substrate was 100 μm.

[0102] [Example 11] When forming a fluorine-containing coating film, a polyfluoroalkyl methacrylate resin (AGC "AG-E060", surface free energy 14 mJ / m ２ A laminate having a functional layer formed on the surface of a substrate was produced in the same manner as in Example 1, except that 100 parts by weight of filler particles (Technopolymer SBX-17 manufactured by Sekisui Plastics Co., Ltd., polystyrene beads, average particle size 17 μm) were added to 100 parts by weight of a polymerizable aqueous dispersion having a solid content of 20% by mass, 60 parts by weight of filler particles, polystyrene beads having an average particle size of 17 μm, and 120 parts by weight of ethanol were added to a mixer (Thinky Corporation's Awatori Rentaro ARV-310), and the mixture was mixed for 1 minute 30 seconds at 2000 rpm to prepare a coating liquid, which was then applied using a #5 bar coater.

[0103] [Example 12] When forming a fluorine-containing coating film, a polyfluoroalkyl methacrylate resin (AGC "AG-E060", surface free energy 14 mJ / m ２A laminate having a functional layer formed on the surface of a substrate was produced in the same manner as in Example 1, except that 100 parts by weight of filler particles (Technopolymer MBX-20 manufactured by Sekisui Chemical Co., Ltd., polymethyl methacrylate resin (PMMA) beads, average particle size 20 μm) were added to 100 parts by weight of a water-based dispersion type having a solid content of 20% by mass, 60 parts by weight of filler particles, and 120 parts by weight of ethanol were added to a mixer (Thinky Corporation's Awatori Rentaro ARV-310), and the mixture was mixed for 1 minute 30 seconds at 2000 rpm to prepare a coating liquid, which was then applied using a #5 bar coater.

[0104] [Example 13] When forming a fluorine-containing coating film, a polyfluoroalkyl methacrylate resin (AGC "AG-E060", surface free energy 14 mJ / m ２ A laminate having a functional layer formed on the surface of a substrate was produced in the same manner as in Example 1, except that 100 parts by weight of filler particles ("HS-103" manufactured by Nippon Steel Chemical & Material Co., Ltd., silica spherical particles, average particle diameter 28 μm) were added to 100 parts by weight of an aqueous dispersion type with a solid content of 20% by mass, and 60 parts by weight of filler particles, and 120 parts by weight of ethanol were added to a mixer ("Awatori Rentaro ARV-310" manufactured by Thinky Corporation), and mixed for 1 minute 30 seconds at 2000 rpm to prepare a coating liquid, which was then applied using a #5 bar coater.

[0105] [Example 14] In forming a fluorine-containing coating film, 100 parts by weight of ethanol was added to 100 parts by weight of fluorine-containing resin ethylene tetrafluoroethylene (ETFE) ("Z8820X" manufactured by AGC, powder form), and the mixture was thoroughly stirred to prepare a coating liquid. This coating liquid was applied using a bar coater #14, and then a laminate having a functional layer formed on the surface of the substrate was produced in the same manner as in Example 1, except that after application of the composite particle-containing dispersion, the coating was dried at 200°C for 60 minutes.

[0106] Example 15 In forming a fluorine-containing coating film, 100 parts by weight of ethylene tetrafluoroethylene ("Z8820X" manufactured by AGC Corporation, powder form), 60 parts by weight of filler particles ("Technopolymer SBX-17" manufactured by Sekisui Plastics Co., Ltd., polystyrene beads, average particle size 17 μm), and 120 parts by weight of ethanol were placed in a mixer ("Awatori Rentaro ARV-310" manufactured by Thinky Corporation), and mixed for 1 minute 30 seconds at 2000 rpm to prepare a coating liquid. This was applied using a #5 bar coater, and then dried at 200°C for 60 minutes after application of the composite particle-containing dispersion. A laminate having a functional layer formed on the surface of the substrate was produced in the same manner as in Example 1, except for this.

[0107] Example 16 A 250 μm thick CPP film (TAISEI CHEMICAL CO., LTD., "TAS-0125") was used as the substrate. In addition, when forming the fluorine-containing coating film, a polyfluoroalkyl methacrylate resin (AGC Co., Ltd., "AG-E060", surface free energy 14 mJ / m ２ A laminate having a functional layer formed on the surface of a substrate was produced in the same manner as in Example 1, except that 100 parts by weight of filler particles (Mipelon (registered trademark) XM221U manufactured by Mitsui Chemicals, Inc., polyethylene beads, average particle size 25 μm) were placed in a mixer (Thinky Corporation's Awatori Rentaro ARV-310), 100 parts by weight of a water-based dispersion having a solid content of 20% by mass, 20 parts by weight of filler particles, polyethylene beads having an average particle size of 25 μm, and 120 parts by weight of ethanol were mixed for 1 minute 30 seconds at 2000 rpm to prepare a coating solution, and the coating solution was applied using a #10 bar coater.

[0108] Example 17 A 100 μm thick PET film ("Emblet SD" manufactured by Unitika Ltd.) was used as the substrate. In addition, when forming the fluorine-containing coating film, a polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC, surface free energy 14 mJ / m ２A laminate having a functional layer formed on the surface of a substrate was produced in the same manner as in Example 1, except that 100 parts by weight of filler particles (Mipelon (registered trademark) XM221U manufactured by Mitsui Chemicals, Inc., polyethylene beads, average particle size 25 μm) were placed in a mixer (Thinky Corporation's Awatori Rentaro ARV-310), 100 parts by weight of a water-based dispersion having a solid content of 20% by mass, 20 parts by weight of filler particles, polyethylene beads having an average particle size of 25 μm, and 120 parts by weight of ethanol were mixed for 1 minute 30 seconds at 2000 rpm to prepare a coating solution, and the coating solution was applied using a #10 bar coater.

[0109] [Example 18] A 20 μm thick soft aluminum foil (1N30, manufactured by Toyo Aluminum K.K.) was coated with a dispersion-type CPP coating agent ("Heat Seal Varnish PPX-16" manufactured by T&K TOKA Corporation, solid content 15% by mass) using a bar coater #14, and dried at 150°C for 60 seconds, resulting in a coating amount of 3 g / m after drying. ２ A primer layer was formed on the soft aluminum foil using a polyfluoroalkyl methacrylate resin (AGC "AG-E060", surface free energy 14 mJ / m) as the fluorine-containing coating film. ２ A laminate having a functional layer formed on the surface of a substrate was produced in the same manner as in Example 1, except that 100 parts by weight of filler particles (Mipelon (registered trademark) XM221U manufactured by Mitsui Chemicals, Inc., polyethylene beads, average particle size 25 μm) were placed in a mixer (Thinky Corporation's Awatori Rentaro ARV-310), 100 parts by weight of a filler particle (Mipelon (registered trademark) XM221U manufactured by Mitsui Chemicals, Inc., polyethylene beads, average particle size 25 μm), and 120 parts by weight of ethanol were mixed for 1 minute 30 seconds at 2000 rpm to prepare a coating liquid, which was then applied onto the primer layer using a #10 bar coater.

[0110] [Example 19] (1) Coating of Fluorine-Containing Resin A commercially available aluminum foil (manufactured by Toyo Aluminum K.K., 1N30, soft aluminum foil, thickness 20 μm) was used as a substrate. In addition, a polyfluoroalkyl methacrylate resin (manufactured by AGC, "AG-E060", surface free energy 14 mJ / m) was used as a fluorine-containing resin. ２To 100 parts by weight of a 20% by weight aqueous dispersion of 20% by weight of ethanol was added 100 parts by weight of ethanol, and the mixture was thoroughly stirred to prepare a coating liquid (dispersion). The coating liquid was applied using a bar coater #5 to a coating weight of 1.0 g / m2 after drying. ２ After coating the surface of the aluminum foil so that the coating liquid satisfies the above-mentioned formula (1), the solvent was evaporated by heating in an oven at 120°C for 40 seconds, thereby forming a fluorine-containing coating film. (2) Preparation of a dispersion containing hydrophobic particles Hydrophobic particles (product name "AEROSIL R812S" manufactured by Evonik Degussa, BET specific surface area: 220 m) were used. ２ 5 g of the hydrophobic particle-containing dispersion (particle size: 1.0 g / g, average primary particle diameter: 7 nm) was dispersed in 100 mL of ethanol to prepare a hydrophobic particle-containing dispersion. (3) Coating of Hydrophobic Particle-Containing Dispersion The obtained hydrophobic particle-containing dispersion was applied to the fluorine-containing coating film using a bar coater #8, and then dried at 120°C for 40 seconds to form a functional layer. The coating amount of the hydrophobic particles in the functional layer was determined by applying the hydrophobic particles in advance to a different substrate using a bar coater under the same conditions and drying the resultant layer to a weight of 2.0 g / m. ２ In this way, a laminate in which a functional layer was formed on the surface of the substrate was produced.

[0111] [Example 20] Hydrophobic particles were coated on a fluorine-containing coating film prepared in the same manner as in Example 19 using a bar coater #24 to a dry weight of 10.0 g / m ２ After coating so as to form the functional layer, the coating was dried at 120°C for 90 seconds.

[0112] [Example 21] Hydrophobic particles were coated on a fluorine-containing coating film prepared in the same manner as in Example 19 using a bar coater #24 to a dry weight of 50.0 g / m ２ The coating and drying under the conditions of 120°C x 90 seconds were repeated five times so as to form a functional layer.

[0113] [Example 22] A commercially available aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, soft aluminum foil, thickness 20 μm) was used as a substrate. The coating liquid prepared in Example 19 was used, and a coating weight of 15.0 g / m was obtained after drying using a bar coater #24. ２After coating the surface of the aluminum foil so that the coating weight was 30.0 g / m, the coating was heated in an oven at 120°C for 40 seconds, and the above process was repeated once more. ２ Next, using the coating liquid of Example 19(2), hydrophobic particles were coated on the fluorine-containing coating film by a bar coater 16 in an amount of 5.0 g / m after drying. ２ After coating so as to form the functional layer, the coating was dried at 120°C for 90 seconds.

[0114] Comparative Example 1 A laminate was produced in the same manner as in Example 1, except that the fluorine-containing resin coating liquid was not applied to the substrate, but only the composite particle-containing dispersion liquid was applied.

[0115] Comparative Example 2 A laminate was produced in the same manner as in Example 1, except that the fluorine-containing resin coating liquid was applied to the substrate, and the composite particle-containing dispersion liquid was not applied.

[0116] [Comparative Example 3] When forming a fluorine-containing coating film, a polyfluoroalkyl methacrylate resin (AGC "AG-E060", surface free energy 14 mJ / m ２ (aqueous dispersion type with a solid content of 20% by mass) was applied to a bar coater #36 to dry and then the weight was 15 g / m ２ After coating so that the coating weight is 30 g / m, the coating is heated and dried in an oven at 120°C for 60 seconds to evaporate the solvent, and this process is repeated twice to obtain a total coating weight of 30 g / m ２ Next, the composite particle dispersion was diluted with ethanol, and the composite particles were coated with a bar coater #3 so that the weight of the composite particles after drying was 0.2 g / m ２ A laminate was produced in the same manner as in Example 1, except that the functional layer was formed by coating the mixture so that the thickness of the coating film was 120° C. and drying was performed under conditions of 120° C. for 40 seconds.

[0117] [Comparative Example 4] When forming a fluorine-containing coating film, a polyfluoroalkyl methacrylate resin (AGC "AG-E060", surface free energy 14 mJ / m ２A coating liquid was prepared by mixing 100 parts by weight of an aqueous dispersion type having a solid content of 20% by weight with 100 parts by weight of ethanol. This coating liquid was used to coat a 0.2 g / m2 film by weight after drying with a bar coater #3. ２ After coating so that the thickness was such that the coating amount was 120° C., the composite particle dispersion was then heated and dried for 40 seconds in an oven at 120° C. Next, the composite particle dispersion was coated using a bar coater #36, dried at 120° C. for 60 seconds, coated again using a bar coater #36, dried at 120° C. for 60 seconds, and further coated using a bar coater #20, dried at 120° C. for 60 seconds, until the coating weight of the composite particles was 50 g / m ２ A laminate was produced in the same manner as in Example 1, except that:

[0118] Comparative Example 5: Instead of the fluorine-containing resin, a maleic anhydride-modified polyolefin resin (MAPO) (product number 290628-2 manufactured by Tanaka Chemical Co., Ltd., surface energy 30 mJ / m ２ A laminate was prepared in the same manner as in Example 1, except that a coating solution of 20% by weight of acrylic resin (solid content: 20%) was used as the coating solution.

[0119] Comparative Example 6 Instead of coating with a fluorine-containing resin, a maleic anhydride-modified polyolefin resin (MAPO) (product number 290628-2 manufactured by Tanaka Chemical Co., Ltd., surface energy 30 mJ / m ２ A laminate was produced in the same manner as in Example 1, except that 100 parts by weight of a coating solution (solid content 20 mass%) was mixed with 20 parts by weight of filler particles ("Mipelon (registered trademark) XM221U" manufactured by Mitsui Chemicals, Inc., polyethylene beads, average particle size 25 μm) and 120 parts by weight of IPA in a mixer ("Awatori Rentaro ARV-310" manufactured by Thinky Corporation), and the mixture was mixed for 1 minute 30 seconds at 2000 rpm to prepare a coating solution, which was then coated using a #10 bar coater.

[0120] Comparative Example 7 A laminate was produced in the same manner as in Example 1, except that a styrene-butadiene rubber-based resin (SBR) ("DYNARON 1320P" manufactured by JSR Corporation) was dissolved in toluene instead of the fluorine-containing resin to form a coating solution with a solid content of 10 mass %, and the coating was carried out using a #20 bar coater.

[0121] Comparative Example 8 A laminate was produced in the same manner as in Example 1, except that an acrylic-modified polyolefin resin (APO) (product number 300214-1 manufactured by Tanaka Chemical Co., Ltd., solid content 20% by mass) was used as the coating liquid instead of the fluorine-containing resin.

[0122] Comparative Example 9 A laminate was produced in the same manner as in Example 1, except that a 50 μm-thick CPP film ("P1011" manufactured by Toyobo Co., Ltd.) was used as the substrate, and an acrylic-modified polyolefin resin (APO) (300214-1 manufactured by Tanaka Chemical Co., Ltd., solid content 20% by mass) was used as the coating liquid instead of the fluorine-containing resin.

[0123] Comparative Example 10 A laminate was produced in the same manner as in Example 19, except that the fluorine-containing resin coating liquid was not applied to the substrate, but only the hydrophobic particle-containing dispersion liquid was applied.

[0124] Comparative Example 11 A laminate was produced in the same manner as in Example 19, except that an acrylic-modified polyolefin resin (APO) (product number 300214-1 manufactured by Tanaka Chemical Co., Ltd., solid content 20% by mass) was used as the coating liquid instead of the fluorine-containing resin coating liquid.

[0125] [Comparative Example 12] A commercially available aluminum foil (manufactured by Toyo Aluminum K.K., 1N30, soft aluminum foil, thickness 20 μm) was used as a substrate. In addition, a coating liquid was used in which an acrylic-modified polyolefin resin (APO) (manufactured by Tanaka Chemical Co., Ltd., 300214-1, solid content 20% by mass) was diluted with IPA to a solid content of 5% by mass, and the coating liquid was applied to the aluminum foil with a bar coater #3 to a weight of 0.1 g / m after drying. ２ Next, the coating solution of Example 19(2) was used to coat the APO coating film with a bar coater #26 so that the hydrophobic particles were coated in an amount of 12.5 g / m after drying. ２ The coating was carried out twice, and the coating was dried at 120°C for 90 seconds. This process was repeated twice, so that the hydrophobic particles had a weight of 25.0 g / m after drying. ２ The functional layer was formed so that

[0126] [Test Example 1] (Cross-Section Observation) The obtained laminate was embedded in epoxy resin and cut at the cross section. The cross section of the cut substrate was irradiated with an Ar ion beam using an ion milling machine (IB-19520CCP, manufactured by JEOL Ltd.) to create a smooth cross section. Next, a scanning electron microscope ("SU8020," manufactured by Hitachi High-Technologies Corporation) was used to confirm the formation of a three-dimensional network structure in which the fluorine-containing resin bridges the composite particles at any point in a plan view. As an example of this observation, a cross-sectional image of the laminate of Example 1 is shown in FIG. 2 , and a cross-sectional image of the laminate of Comparative Example 1 is shown in FIG. 3 . As a result of the observation, when a three-dimensional network structure in which the fluorine-containing resin bridges the functional particles was formed, it was marked with "◯," and when such a three-dimensional network structure was not formed, it was marked with "X." Therefore, for example, when the fluorine-containing resin did not bridge the functional particles and the three-dimensional network structure was formed only from the functional particles, it was marked with "X."

[0127] [Test Example 2] (Measurement of Specific Surface Area) The specific surface area of ​​each laminate sample was measured using a NOVA 1000e specific surface area analyzer manufactured by Quantachrome Instruments Incorporated according to the static capacitance method specified in Japanese Industrial Standard JIS Z8830:2013, as follows. The results are shown in Table 2. (1) Laminate Packing Method: Sampling was performed by cutting a 100 mm long x 100 mm wide laminate into 10 mm width pieces and packing them into a specified glass tube. Careful cutting and packing were performed to prevent the functional layer from falling off. (2) Laminate Pretreatment: The sample was pretreated in a vacuum at 100°C for 1 hour using the specific surface area analyzer, and gases such as water vapor were removed in advance. (3) Laminate Specific Surface Area Measurement: An adsorption isotherm for the laminate was created under the following conditions. - Adsorption gas: High-purity compressed nitrogen gas (manufactured by Air Water West Japan Inc., Amagasaki Plant, purity 99.999% or more) - Adsorption temperature: 77.35K - Pressure tolerance: 0.100mmHg / 0.100mmHg (adsorption / desorption) - Equilibration time: 60 seconds / 60 seconds (adsorption / desorption) - Equilibration timeout: 240 seconds / 240 seconds (adsorption / desorption) - Measurement range: 0.05<relative pressure P / P0<0.3 - Thermal delay: 180 seconds - Evacuation cross-over pressure: 20mmHg The specific surface area of ​​the laminate was calculated from the adsorption isotherm of the obtained laminate using the BET multi-point method. In this case, the condition was that the correction coefficient r, which indicates the accuracy of the obtained adsorption isotherm, was 0.9999 or more and the number of measurement plots was 4 or more. If r was less than 0.9999 even with the number of measurement plots of 4, the number of samples was increased by one each time and the procedure was repeated until r became 0.9999 or more. (4) Calculation of the specific surface area of ​​the functional layer The specific surface area St (m ２ / g) to obtain the specific surface area S (m ２ / g) can be calculated from the formula "S = St / (W1 / Wt)". Here, (W1 / Wt) is the weight ratio of the functional layer formed on the surface layer of the laminate, Wt is the weight of the laminate, and W1 is "weight of the laminate - weight of the substrate". In this way, the specific surface area of ​​the functional layer was calculated. The results are shown in Table 2.

[0128] [Test Example 3] (Measurement of porosity) A substrate was embedded in an epoxy resin, and the substrate was cut at its cross section. The cross section of the cut substrate was irradiated with an Ar ion beam using an ion milling device ("IB-19520CCP" manufactured by JEOL Ltd.) to create a smooth cross section. Next, using a scanning electron microscope ("SU8020" manufactured by Hitachi High-Technologies Corporation), the sample cross section was observed under conditions of an electron emission current of 4300 nA, a working distance of 3.0 mm, and a magnification of 30,000 times, with a field of view of 12 μm. ２ A secondary electron image of the functional layer was obtained. When capturing the secondary electron image, the optimal focus was adjusted to minimize astigmatism, and the brightness and contrast were adjusted until optimal appearance was achieved to prevent clipping phenomena such as overexposure. The sample was then appropriately vapor-deposited using a vapor deposition device (JFC-1600 manufactured by JEOL Ltd.) to prevent the image from becoming blurred due to charging by the electron beam, and then observed. When capturing the image, the sample position was adjusted so that the functional layer was captured across the entire field of view, assuming that the image would be appropriately processed using image processing software. The region from the bottom of the functional layer to 50% of the thickness was defined as the "bottom," and the region from the bottom of the functional layer to the surface of the functional layer beyond 50% of the thickness was defined as the "top." The obtained secondary electron image was then binarized using the image processing software "WinROOF2018ver4.25," and the total number of pixels in the three-dimensional network structure portion of the secondary electron image was measured. The porosity was calculated as "100% - (binarized proportion (%) of the three-dimensional network structure portion)." The binarization was performed using the automatic binarization system of the software, selecting a bright area as the extraction area, and then using discriminant analysis. The threshold value was set according to the automatic binarization system and was not changed. In this way, the visual field range was 12 μm ２The porosity was calculated from the ratio of the total number of pixels in the three-dimensional mesh structure to the total number of pixels per unit area. The results are shown in Table 2. This operation was repeated 20 times for each of the bottom and top parts, and the average value was used as the porosity. As an example, the binarized image of Example 1 is shown in Figure 4.

[0129] [Test Example 4] (Measurement of Surface Free Energy) The surface free energy of the fluorine-containing resin was measured using a contact angle meter ("DMo-702" manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 2. In the Examples and Comparative Examples, a fluorine-containing resin coated sample prior to application of a functional particle dispersion or the like was used as the test sample. The test sample was placed on the stage of the contact angle meter with the fluorine-containing resin coated side facing upward and free of wrinkles. Applying the Owens-Wendt theory, pure water and diiodomethane were used as probe liquids, and 1 microliter of the liquid was dropped onto the fluorine-containing resin side. The contact angle was calculated automatically using the KYOWA InterFace Measurement and Analysis System (FAMAS) software from 10 seconds later. These methods were repeated three times, and the average value was used. The surface free energy of the fluorine-containing resin in each Example and Comparative Example was also measured using the same method. The results are shown in Table 2.

[0130] [Test Example 5] (Oil-repellent durability and water-repellent durability) (1) Oil-repellent durability A commercially available edible oil with a known surface tension (Nissin Salad Oil Cholesterol 0, manufactured by The Nisshin Oillio Group, Ltd., surface tension 32 mJ / m ２ ) was placed in a 100 mL glass bottle. Next, this glass bottle was placed on a hot stirrer, a stirrer bar was inserted, and the mixture was stirred at a speed of 50 rpm while waiting until it stabilized at 90°C. After that, a 20 mm x 20 mm sample was secured with a clip and immersed in the above-mentioned edible oil at 90°C. At this time, the position of the sample was adjusted so that it would not come into contact with the stirrer. After 2 hours of immersion, the sample was removed and immersed in a commercially available olive oil with a known surface tension (surface tension 32 mJ / m ２) was dropped onto the functional layer surface, and the state of the droplet was confirmed. Specifically, the test surface was tilted at an angle of 20 degrees or 45 degrees, and 1 mL of olive oil was dropped onto it. Evaluation was performed as follows: if the olive oil dropped completely rolled off even at a 20-degree tilt, it was marked with "◎"; if the olive oil dropped completely rolled off at a 45-degree tilt but not at a 20-degree tilt, it was marked with "◯"; if the olive oil dropped partially rolled off at a 45-degree tilt, it was marked with "△"; and if the olive oil dropped completely did not roll off at a 45-degree tilt, it was marked with "×". The results are shown in Table 2. Separately, the edible oil in the glass bottle was heated to 100°C, and the sample was immersed in this edible oil. After immersion for one hour, the sample was removed and again immersed in commercially available olive oil with a known surface tension (surface tension 32 mJ / m ２ ) was dropped onto the surface of the functional layer, and the state of the droplets was confirmed. The evaluation method was the same as in the case of 90°C x 2 hours described above, and the results were evaluated as "◎", "◯", "△", or "X". The results are shown in Table 2. (2) Water-repellent durability 80 mL of distilled water was placed in a 100 mL glass bottle. Next, this glass bottle was placed on a hot stirrer, a stirrer bar was inserted, and the mixture was stirred at a speed of 50 rpm while waiting until it stabilized at 80°C. After that, a 20 mm x 20 mm sample was secured with a clip and immersed in the above-mentioned hot water at 80°C. The position of the sample was adjusted so that it would not come into contact with the stirrer. 30 minutes after immersion, the sample was removed and rehydrated in ion-exchanged water (surface tension 72 mJ / m ２ ) was dropped onto the surface of the functional layer, and the state of the droplet was confirmed. Specifically, the test surface was tilted at an angle of 20 degrees or 45 degrees with the test surface facing up, and 1 mL of water droplet was dropped. If the dropped water droplet completely rolled even at a 20-degree tilt, it was marked as "◎", if the dropped water droplet did not completely roll at a 20-degree tilt but completely rolled at a 45-degree tilt, it was marked as "◯", if the dropped water droplet partially rolled at a 45-degree tilt, it was marked as "△", and if the dropped water droplet did not roll at all at a 45-degree tilt, it was marked as "×". The results are shown in Table 2.

[0131]

[0132]

[0133] As is clear from the results in Table 2, the laminates of Examples 1 to 18 using composite particles can maintain good oil repellency even when immersed in high-temperature oil. This suggests that high oil repellency can be achieved even when oil adheres to the functional layer due to long-term use of the laminate, and the functional layer is immersed in oil.

[0134] In particular, among the examples, the surface free energy of the fluorine-containing resin is 32 mJ / m ２ Among those in which the difference is large compared to the above and the specific surface area is close to the value of the inorganic oxide fine particles alone, it can be seen that the effect is particularly remarkable when the weight ratio of the functional particles to the fluorine-containing resin is 1:3 to 4:1.

[0135] It is also apparent that the laminates of Examples 19 to 22, which used hydrophobic particles, were able to maintain good water repellency even when immersed in hot water.

Claims

1. A laminate including a substrate and a functional layer, (1) The functional layer includes a three-dimensional mesh structure, (2) The three-dimensional network structure includes (a) at least one type of functional particle selected from (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) hydrophobic particles, and (b) a fluorine-containing hydrophobic resin; (3) The specific surface area of ​​the functional layer is 2 to 195 m 2 / g; A laminate characterized by:

2. 2. The laminate according to claim 1, wherein the functional particles are fixed to the three-dimensional network structure by a fluorine-containing hydrophobic resin.

3. 2. The laminate according to claim 1, wherein the functional layer is supported on the substrate by the fluorine-containing hydrophobic resin adhering to the substrate and the functional particles.

4. The laminate described in claim 1, wherein the porosity of the region of the functional layer from the bottom surface to 50% of the thickness is 0 to 45%, and the porosity of the region from the bottom surface of the functional layer to more than 50% of the thickness to the surface (outermost surface) of the functional layer is 10 to 55%.

5. 2. The laminate according to claim 1, wherein a ratio of the functional particles to the fluorine-containing hydrophobic resin (excluding the fluorine-containing hydrophobic resin contained in the functional particles) is 1:50 to 20:1 by weight of solids.

6. 2. The laminate according to claim 1, wherein the fluorine-containing hydrophobic resin is at least one selected from the group consisting of polyfluoroalkyl methacrylate resin, polytetrafluoroethylene, and ethylene tetrafluoroethylene.

7. 2. The laminate according to claim 1, wherein the substrate is at least one selected from the group consisting of metal foil, metal plate, resin film, resin plate, paper, wood board, nonwoven fabric, and primer-coated versions of these.

8. 2. The laminate according to claim 1, wherein the inorganic oxide fine particles have an average primary particle size of 5 to 50 nm.

9. 2. The laminate according to claim 1, wherein the three-dimensional network structure further comprises filler particles having an average particle diameter D50 of 5 to 60 μm.

10. A method for producing the laminate of claim 1, comprising: (1) A step of forming a fluorine-containing coating film by applying a fluorine-containing coating liquid containing a fluorine-containing hydrophobic resin to a substrate; and (2) A step of forming a composite particle-containing coating film by applying to the fluorine-containing coating film (a) a coating liquid containing at least one kind of functional particles, namely (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles, and (a2) hydrophobic particles. A method for producing a laminate, comprising:

11. A manufacturing method described in claim 10, wherein the ratio of functional particles to fluorine-containing hydrophobic resin (excluding the fluorine-containing hydrophobic resin contained in the functional particles) is 1:50 to 20:1 by solid weight ratio.