TW202405255A - Laminated body - Google Patents

Abstract

An object of the present invention is to provide a laminated body capable of maintaining good water repellency or oil repellency even when the body is in contact with oil or water for a long period of time. The present invention relates to a laminated body comprising a substrate and a functional layer, wherein (1) the functional layer includes a three-dimensional network structure, (2) the three-dimensional network structure has (a) at least one functional particle selected from the group consisting of (a1) a composite particle comprising an inorganic oxide fine particle and a coating layer containing a polyfluoroalkylmethacrylate resin formed on the surface of the inorganic oxide fine particle and (a2) a hydrophobic particle and (b) a fluorine-containing hydrophobic resin.

Description

laminated body

The present invention relates to a novel laminated body. More specifically, it relates to a laminate having water-repellent and oil-repellent properties.

Water-repellent technology or oil-repellent technology is being widely studied for anti-adhesion applications, mold release applications, and the like. In particular, for food, beverages, pharmaceuticals, cosmetics, etc., in order to prevent or suppress the adhesion of contents to packaging materials, products are being developed that are subjected to super-water-repellent treatment with a contact angle of 150° or more with water. Or super oil-repellent treatment with a contact angle of more than 150° with oil.

For example, there is known a laminate (Patent Document 1) in which a porous functional layer is formed on a base film, and the porous functional layer includes fine particles having water-repellent and/or oil-repellent properties that are firmly adhered to each other. The three-dimensional network structure and the thermoplastic resin formed by 1 volume % or more and 50 volume % or less, and the void ratio in the area from the bottom of the porous functional layer exceeding 50% of the thickness to the porous functional layer surface is 50 volume % or more and 99 volume % or less. Prior technical literature patent documents

Patent Document 1: Japanese Patent Application Publication No. 2021-146651

The problem to be solved by the invention As in the above-mentioned conventional technology, since the three-dimensional network structure has a predetermined porosity, the fine particles are not easy to fall off, and can exhibit high water repellency and oil repellency. However, if it is used in contact with oil or moisture for a long time, the three-dimensional network structure may be immersed in the oil, and the water-repellent or oil-repellent properties may be reduced.

Therefore, the main object of the present invention is to provide a laminate with consistently good water-repellent or oil-repellent properties.

means to solve problems In view of the problems of the conventional technology, the inventor repeatedly and actively researched and found that a laminated body with a specific composition and structure can achieve the above purpose, and finally completed the present invention.

That is, the present invention relates to the following laminated body. 1. A laminate including a base material and a functional layer, characterized in that: (1) the functional layer includes a three-dimensional network structure; and (2) the three-dimensional network structure includes: (a) functional particles and (b) Fluorine-containing hydrophobic resin, the (a) functional particles are at least one of (a1) composite particles and (a2) hydrophobic particles, and the (a1) composite particles have polyfluorine-containing methacrylic acid particles on the surface of the inorganic oxide particles. Alkyl ester resin coating. 2. The laminate according to the above item 1, wherein the functional particles are fixed in the three-dimensional network structure by a fluorine-containing hydrophobic resin. 3. The laminated body according to the above item 1, wherein the functional layer is supported on the base material by bonding the base material and the functional particles with a fluorine-containing hydrophobic resin. 4. The laminated body as described in item 1 above, wherein the specific surface area of the functional layer is 2 to 195 m ² /g. 5. The laminated body as described in Item 1 above, wherein in the functional layer, the void ratio in the area from the bottom of the functional layer to 50% of the thickness is 0 to 45%, and the void ratio from the bottom of the functional layer to more than 50% of the thickness of the functional layer is 0 to 45%. The void ratio of the area on the surface of the layer (the most surface) is 10~55%. 6. The laminate of item 1 above, wherein the ratio of the functional particles to the fluorine-containing hydrophobic resin (excluding the fluorine-containing hydrophobic resin contained in the aforementioned functional particles) is 1 based on the solid content weight ratio. :50~20:1. 7. The laminated body according to the above 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 laminated body as described in item 1 above, wherein the base material is selected from the group consisting of metal foil, metal plate, resin film, resin board, paper, wood board, non-woven fabric or primer coat thereof. Make up at least one of the groups. 9. The laminate as described in item 1 above, wherein the average primary particle size of the inorganic oxide particles is 5 to 50 nm. 10. The laminated body as described in item 1 above, wherein the three-dimensional network structure further contains filling particles with an average particle diameter D50 of 5 to 60 μm. 11. A method for manufacturing a laminated body, which is a method for manufacturing a laminated body including a base material and a functional layer, characterized by comprising: (1) a step of forming a fluorine-containing coating film by coating the base material with a fluorine-containing coating film and (2) the step of forming a coating film containing composite particles by applying a coating liquid containing (a) functional particles to the aforementioned fluorine-containing coating film. , the (a) functional particles are at least one of (a1) composite particles and (a2) hydrophobic particles, and the (a1) composite particles have a coating containing polyfluoroalkyl methacrylate resin on the surface of the inorganic oxide fine particles. layer.

Invention effect According to the present invention, it is possible to provide a laminated body with consistently good water-repellent properties and/or oil-repellent properties. That is, it is possible to provide a laminate having more excellent water-repellent properties and/or oil-repellent properties and durability (oil-repellent durability, etc.).

In particular, the laminate of the present invention includes a three-dimensional network structure including functional particles and (b) fluorine-containing hydrophobic resin, and the functional particles are (a1) composite particles and (a2) hydrophobic resin. At least one kind of particles, and the (a1) composite particles have a coating layer containing polyfluoroalkyl methacrylate resin on the surface of the inorganic oxide fine particles, so they have high dispersion caused by the two components of the aforementioned functional particles and the hydrophobic resin. Water-based and oil-repellent properties, and because the functional particles are relatively tightly fixed to the three-dimensional network structure and the base material, it can also inhibit or prevent the functional particles from falling off over time. As a result, the water-repellent properties and/or oil-repellent properties can be affected. Oil properties impart high durability. Therefore, it can still exhibit high water-repellent and/or oil-repellent properties even if it is exposed to oil or moisture for a long time. In particular, for example, even when the functional layer is immersed in oil (for example, oil at a high temperature above 50°C), good water repellency or oil repellency can still be obtained, and this effect can be sustained over a long period of time.

1.Laminated body of the present invention The laminated body of the present invention includes a base material and a functional layer, and is characterized by: (1) The functional layer contains a three-dimensional network structure; and (2) The three-dimensional network structure includes: (a) functional particles and (b) fluorine-containing hydrophobic resin, and the (a) functional particles are at least one of (a1) composite particles and (a2) hydrophobic particles, Furthermore, the composite particles (a1) are provided with a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of the inorganic oxide fine particles.

An example of an embodiment of the laminated body of the present invention is shown in FIG. 1 . The laminated body 10 in FIG. 1 is directly connected to the base material 11 to form the functional layer 12. As shown in FIG. 1 , the functional layer 12 includes a three-dimensional network structure 12 a. The functional layer 12 shown in Figure 1 may also include gaps 12b.

The three-dimensional network structure 12a in Figure 1 includes: functional particles A and fluorine-containing hydrophobic resin (hereinafter referred to as "fluorine-containing resin") B. The functional particles A are (a1) composite particles and (a2) hydrophobic At least one of the inorganic oxide particles, and the composite particle (a1) is provided with a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of the inorganic oxide fine particles. In other words, a plurality of functional particles are firmly connected to each other in the form of bridging with fluorine-containing resin, thereby forming a three-dimensional network structure. In this way, the functional particles are fixed in the three-dimensional network structure by the fluorine-containing resin. The state thus presented is that the functional particles A are fixed to the functional layer 12 and the functional layer 12 is fixed to the base material 11 . In other words, the functional layer 12 is supported on the base material by bonding the base material 11 and the functional particles A with the fluorine-containing resin. At this time, even if hydrophobic particles are used instead of functional particles, a plurality of hydrophobic particles will be firmly connected to each other in the form of fluorine-containing resin bridges, thereby forming a three-dimensional network structure, and high dial properties can be obtained. Water-based and durable.

As shown in FIG. 1 , a plurality of functional particles A (particle groups) are mainly composed of a state in which they are aggregated with each other through the fluorine-containing resin. At this time, the state is that the plurality of functional particles A have fluorine-containing resin interposed therebetween. However, the gaps 12b may be included between the functional particles within a range that does not hinder the effect of the present invention. In addition, the functional particles A are usually indirectly connected to each other through the fluorine-containing resin B, but the functional particles may be directly connected to each other within the scope that does not hinder the effect of the present invention.

For example, the structure of Comparative Example 1 is shown in FIG. 3 , and a three-dimensional network structure body composed of functional particles is formed. That is, functional particles (composite particles) adhere to each other mainly through intermolecular forces to form a three-dimensional network structure (the fluororesins on each surface of adjacent functional particles are not bonded in a bridging manner even if they are in contact with each other) Knot (strongly bonded). In contrast, as shown in Figure 2 of Example 1, functional particles (composite particles) are bonded (strongly bonded) with each other by cross-linking with fluorine-based resin, thereby forming a three-dimensional network structure. . In this point, the three-dimensional network structure of the present invention is different from a three-dimensional network structure substantially composed only of functional particles. Each structure of the laminate of the present invention will be described in detail below.

(1)Substrate The base material mainly functions as a supporting layer that supports the functional layer. Therefore, the material is not particularly limited as long as it has the above function, and examples thereof include metal foil (for example, aluminum foil, etc.), metal plate (steel plate, etc.), resin film (for example, synthetic resin such as polyester, polyethylene, and polypropylene), Resin board (such as polyester, polyethylene, polypropylene and other synthetic resins), paper, wood board, non-woven fabric or their primer coatings.

In particular, in the present invention, for example, at least one resin film selected from a polypropylene film, a polyethylene film, and a polyester film, or a metal foil (especially an aluminum foil) can be suitably used as the base material.

When the base material is a resin film, the resin film may be either a stretched film or an unstretched film. In addition, as the stretched film, either a uniaxially stretched film or a biaxially stretched film can be used. In addition, resin films, for example, various types of resin films that have been subjected to surface treatment such as corona treatment, can also be used as the base material.

The thickness of the base material is not limited and can be appropriately set depending on, for example, the material of the base material, the use of the laminate of the present invention, and the like. When the substrate is in the form of a film or the like, generally speaking, it can be appropriately set within the range of about 20 to 80 μm, but it is not limited to this.

The substrate may also be subjected to surface treatment on its surface (especially the surface where the functional layer is laminated). This can further improve the adhesion (adhesion) between the base material and the functional layer. Examples of the surface treatment include uneven treatment using additives (preferably filler particles), uneven treatment using embossing, and the like. The height of the concavities and convexities is not limited, but is preferably about 5 to 60 μm, with 20 to 50 μm being more suitable. Here, as the filling particles, those shown below may be used.

(2)Functional layer The functional layer is a layer with water-repellent and/or oil-repellent properties. A functional layer is formed on at least one side of the substrate.

The functional layer has a three-dimensional network structure. The three-dimensional network structure includes: (a) functional particles and (b) fluorine-containing hydrophobic resin. The (a) functional particles are (a1) composite particles and (a2) At least one kind of hydrophobic particles, and the (a1) composite particles are provided with a coating layer containing polyfluoroalkyl methacrylate resin on the surface of the inorganic oxide fine particles. By having such a structure, it can exhibit water repellency or oil repellency and prevent or inhibit the adhesion of objects to the functional layer.

Since the aforementioned functional layer has a three-dimensional network structure and can take a porous form, it has a predetermined specific surface area. The specific surface area at this time is not limited, and usually the specific surface area should be about 2~195m ² /g. Therefore, it can also be set to about ² ~55m2/g, for example. This can also be an indicator of the degree of bridging between the fluorine-containing resin and the functional particles in the three-dimensional network structure of the functional layer. In addition, the specific surface area in the present invention shows the specific surface area of the BET method (Brunauer-Emmett-Teller method: Boet method).

The relationship between the structure of the functional layer and the specific surface area is explained below with specific numerical values as an example for easy understanding. The specific surface area of the functional layer is the largest when only functional particles are coated on the base material. For example, when only functional particles are applied to a substrate and the specific surface area is measured, the result is approximately 200 m ² /g. This is a three-dimensional network structure formed by functional particles only by intermolecular forces. If the void ratio is measured to be about 55% using the method of Test Example 3 described below, theoretically it will be the state in which the functional layer retains the most voids. Since the functional layer composed only of functional particles only uses intermolecular forces to form a three-dimensional network structure, the functional particles may fall off easily. The critical point is a specific surface area of about 195 m ² /g. If it exceeds about 197 m ² /g, the amount of fluorine-containing resin is insufficient, so the possibility of functional particles falling off becomes high.

In addition, when the functional layer is composed of only fluorine-containing resin and no functional particles are present, it becomes a smooth surface and has the lowest specific surface area. For example, even if polyfluoroalkyl methacrylate resin is only coated on the base material, the void ratio is 0% and the specific surface area is the lowest of about 0.2m ² /g. At this time, the three-dimensional network structure is almost destroyed, and the surface air portion becomes a functional layer with less air, and sufficient oil repellent durability may not be obtained. In addition, the critical point of the specific surface area is about 2 m ² /g. If it is lower than the critical point of about 1 m ² /g, there will be almost no voids, and the oil-repellent durability or water-repellent durability may be deteriorated.

From the above, it can be seen that there is a certain correlation between the void ratio and the specific surface area of the functional layer. The void (i.e., air layer) is theoretically said to repel material the most, and we judge that the contact angle with respect to water or oil is 180°. According to the Cassie-Baxter theory, it is said that the mosaic structure of the air layer and individual substances depends on the proportion of the air layer and the liquid-repellent ability of the individual substances themselves.

As mentioned above, even if the porosity is set to the maximum, when the functional particles are formed by only intermolecular forces, the functional particles are easy to fall off, so the material used to maintain the three-dimensional network structure is important. Therefore, in the present invention, a fluorine-containing hydrophobic resin is used to support the functional particles. When a substance other than the above-mentioned fluorine-containing resin is used as the resin that bridges the functional particles, sufficient oil-repellent durability or water-repellent durability will not be obtained. We judge that this is because generally speaking, the surface free energy (individual surface tension) of fluorine-containing substances is as low as about 20 mJ/m ² or less, which is sufficient for the surface tension of 32 mJ/m ² of the edible oil used in Test Example 5 described below. Have gaps. On the other hand, the surface free energy of fluorine-free resins such as olefins and styrene-butadiene rubber is about 30~34mJ/ ^m2 , which is slightly different from the surface tension of edible oil, which is 32mJ/ ^m2 . Therefore, we judge that it is easily wetted by oil, and the oil-repellent durability or water-repellent durability becomes low. In this regard, the surface free energy of the fluorine-containing resin used in the present invention is usually about 5 to 25 mJ/m ² , and more preferably about 5 to 20 mJ/m ² .

Considering the oil-repellent durability or water-repellent durability, it is expected to be reinforced by bridging functional particles with fluorine-containing resin and maintaining a predetermined gap. Furthermore, when a fluorine-containing hydrophobic resin is not used as the resin, it becomes difficult to fully exhibit oil repellency or water repellency. From the viewpoint of oil repellency or water repellency, the larger the void ratio, the better. However, if the void ratio is too large, the physical structure will tend to gradually become brittle. At this time, fluorine-containing resin is embedded at the bottom. Even if the void ratio is 0%, if the void ratio in the upper part is more than 10%, the oil repellency or water repellency can be maintained.

On the other hand, when the void ratio at the bottom is 0% and the void ratio at the upper part is 2%, sufficient oil repellency or water repellency may not be obtained because there are too few voids. Even if the void ratio at the bottom is 0% and the void ratio at the top is 10%, although the effect is not good, the desired oil-repellent or water-repellent properties can still be maintained.

Here, the above-mentioned "bottom" refers to the area from the bottom of the functional layer on the base material side to 50% of the thickness of the functional layer as shown in Figure 1. The above-mentioned "upper part" refers to the area in the functional layer from more than 50% of the thickness of the bottom surface of the functional layer to the surface (outermost) of the functional layer, as shown in Figure 1.

On the other hand, the maximum void ratio is 55% at the bottom and 55% at the top when only functional particles are coated. As mentioned above, since functional particles are essentially only bonded by intermolecular forces, they may fall off easily. When the void ratio is 45% at the bottom and 55% at the top, the oil-repellent durability or water-repellent durability is insufficient at the critical point but can still be maintained. When the void ratio exceeds the above, it is speculated that the degree of bridging using fluorine-containing resin is not sufficient, and the void ratio is 53% at the bottom and 55% at the top, and the oil-repellent durability or water-repellent durability may not be maintained. From the above point of view, the void ratio can be set in the range of about 0 to 45% at the bottom and about 10 to 55% at the top. It is especially suitable to set it to 31 to 45% at the bottom and 40 to 55% at the top. Among them, it is also more suitable to set it to 35~41% at the bottom and 44~48% at the top. In particular, the functional layer should have an inclined structure in which the porosity gradually increases from the bottom to the top. Therefore, it is ideal for the void ratio at the top to be larger than the void ratio at the bottom. For example, the difference between the two [(void ratio at the top) - (void ratio at the bottom)] is usually more than 3%, especially 4 to 15%.

The ratio of functional particles and fluorine-containing resin (excluding the fluorine-containing hydrophobic resin contained in the aforementioned functional particles) in the three-dimensional network structure is usually set to 1:50~20 in terms of solid content weight ratio. : Around 1, it is especially suitable to set it in the range of 1:30~20:1, and more preferably in the range of 1:10~4:1, among which 1:3~4:1 is the best. By setting it within the above range, a three-dimensional network structure can be formed in which the functional particles are tightly bridged with the hydrophobic resin containing fluorine. At this time, if the ratio of fluorine-containing resin continues to increase and exceeds 1:30 and there is too much fluorine-containing resin, the fluorine-containing resin bridging the functional particles will fill the gaps between the functional particles, making it impossible to maintain the three-dimensional network structure. . This makes the physical properties equivalent to those of merely coating the fluorine-containing resin on the base material, and sufficient oil repellency or water repellency cannot be obtained. This means that the specific surface area gradually becomes closer to the value when the fluororesin coating film is applied to the base material. On the other hand, we judge that if the ratio exceeds 20:1 and there are too many functional particles, it will be close to a coating film containing only functional particles. Since the fluorine-containing resin cannot bridge the functional particles with each other, sufficient strong adhesion cannot be obtained. However, it cannot exhibit oil-repellent durability or water-repellent durability.

(2-1)Hydrophobic particles As the hydrophobic particles, for example, at least one kind of inorganic oxide particles (powder) such as silicon oxide, titanium oxide, aluminum oxide, and zinc oxide can be used. Among them, silicon oxide particles are also preferred.

In addition, the hydrophobic particles can also be used, for example, hydrophilic fine particles that have been hydrophilized by etching, ultraviolet irradiation, sand blasting, plasma treatment, etc., are hydrophobicized with a silane coupling agent, etc., so that the hydroxyl group is partially left. . By forming the functional layer with a three-dimensional network structure, the surface on the primer layer side can be strongly bonded to the thermosetting resin, and the other surface can exhibit super water repellency and/or super oil repellency.

The average primary particle diameter of the inorganic oxide particles is preferably 5 to 50 nm, and 7 to 30 nm is particularly ideal. In addition, the average particle size of the primary particles of the inorganic oxide particles can be measured using a transmission electron microscope or a scanning electron microscope. More specifically, the average primary particle size is determined by taking a photo with a transmission electron microscope or a scanning electron microscope, measuring the diameters of more than 200 particles on the photo, and calculating the arithmetic mean value.

The aforementioned nanoscale inorganic oxide particles are not limited, and well-known or commercially available ones can also be used. Examples of silicon oxide include product names "AEROSIL R972", "AEROSIL R972V", "AEROSIL R972CF", "AEROSIL R974", "AEROSIL RX200", "AEROSIL RY200" (the above, manufactured by Nippon Aerosil Co., Ltd.), " AEROSIL R202", "AEROSIL R805", "AEROSIL R812", "AEROSIL R812S", (above, manufactured by Evonik Degussa Co., Ltd.), "SYLOPHOBIC100", "SYLOPHOBIC200", "SYLOPHOBIC603" (above, manufactured by Fuji Silysia Chemical Ltd. )wait. Examples of titanium oxide include product name "AEROXIDE TiO ₂ T805" (manufactured by Evonik Degussa Co., Ltd.). Examples of alumina include fine particles whose product name is "AEROXIDE Alu C" (manufactured by Evonik Degussa Co., Ltd.), etc., which are treated with a silane coupling agent to make the particle surface hydrophobic.

Among these, hydrophobic silicon oxide fine particles can also be suitably used. In particular, hydrophobic silicon oxide fine particles having a trimethylsilyl group on the surface are preferred because they can obtain relatively excellent non-adhesion properties. Examples of corresponding commercially available products include the aforementioned "AEROSIL R812" and "AEROSIL R812S" (both manufactured by Evonik Degussa Co., Ltd.).

The attached amount of hydrophobic particles (weight after drying) is not limited, but can usually be set in the range of about 0.01~100g/ ^m2 , especially preferably 0.01~50g/ ^m2 , 0.1~50g/ ^m2 Better, among which 2~10g/ ^m2 is the best.

(2-1)Composite particles The composite particles are characterized by having a coating layer containing polyfluoroalkyl methacrylate resin on the surface of the inorganic oxide fine particles. That is, composite particles have inorganic oxide fine particles as core particles, and a coating layer containing polyfluoroalkyl methacrylate resin is formed on the surface of the core particles.

The inorganic oxide fine particles used as the core particles are not particularly limited, and for example, at least one of particles (powders) such as silicon oxide, titanium oxide, aluminum oxide, and zinc oxide can be used appropriately. Among them, silicon oxide particles are also suitable.

The size of the inorganic oxide particles is not limited, but usually the average primary particle size is about 5 to 50 nm, especially 7 to 30 nm. In addition, the measurement of the average particle diameter of the primary particles can be carried out using a transmission electron microscope or a scanning electron microscope. More specifically, the average primary particle size is determined by taking a photo with a transmission electron microscope or a scanning electron microscope, measuring the diameters of more than 200 particles on the photo, and calculating the arithmetic mean value.

As the aforementioned nanoscale inorganic oxide particles, known or commercially available ones can be used. Examples of silicon oxide are: product name "AEROSIL 200"("AEROSIL" is a registered trademark. The same applies below), "AEROSIL 130", "AEROSIL 300", "AEROSIL 50", "AEROSIL 200FAD", "AEROSIL 380" (above) , Nippon Aerosil Co., Ltd.), etc. Examples of titanium oxide include product name "AEROXIDE TiO ₂ T805" (manufactured by Evonik Degussa Co., Ltd.). Examples of alumina include the product name "AEROXIDE Alu C 805" (manufactured by Evonik Degussa Co., Ltd.).

The preparation method of the composite particles is not particularly limited. For example, polyfluoroalkyl methacrylate resin is used as a coating material for inorganic oxide fine particles (powder), and the coating layer is formed according to known coating methods, granulation methods, and the like. More specifically, the composite particles can be appropriately prepared by a manufacturing method including a step of applying a coating liquid that contains liquid methacrylic acid to the inorganic oxide fine particles (coating step). The fluoroalkyl ester resin is dissolved or dispersed in the solvent.

As the resin, a known or commercially available resin can be used. Examples of commercially available products include: product name "CHEMINOX FAMAC-6" (manufactured by Unimatec (Japan) Co., Ltd.), product name "Zonyl TH Fluoromonomer code 421480" (manufactured by SIGMA-ALDRICH (USA) Co., Ltd.), product name "SCFC-65530" -66-7" (manufactured by Maya High Purity Chem (CHINA) Co., Ltd.), product name "FC07-04~10" (Fluory, Inc (USA)), product name "CBINDEX:58" (Wilshire Chemical Co., Inc( USA) company), product name "AsahiGuard AG-E530", "AsahiGuard AG-E060" (both manufactured by Asahi Glass Co., Ltd.), product name "TEMAc-N" (Top Fluorochem Co., LTD (CHINA ) company), product name "Zonyl 7950" (manufactured by SIGMA-RBI (SWITZ) Co., Ltd.), product name "6100840~6100842" (manufactured by Weibo Chemical Co., Ltd (CHINA)), product name "CB INDEX: 75 ” (made by ABCR GmbH&CO.KG (GERMANY)), etc.

In the above-mentioned production method, what is liquid at normal temperature (25° C.) and normal pressure can be suitably used as the polyfluoroalkyl methacrylate resin. The polyfluoroalkyl methacrylate resin may also be commercially available as described above. Among these, from the viewpoint of achieving relatively excellent water repellency and oil repellency, for example, a) polyfluorooctyl methacrylate, b) 2-N,N-diethylamine methacrylate can be suitably used. The resin is a copolymer of ethyl ester, c) 2-hydroxyethyl methacrylate and d) 2,2'-ethylenedioxydiethyldimethacrylate. Commercially available products can also be used.

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

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

The method of applying the coating liquid to the surface of the inorganic oxide fine particles is preferably a well-known method, and any of the spraying method, dipping method, stirring granulation method, etc. can be used. In particular, in the present invention, in view of excellent points such as uniformity, coating by a spray method is particularly preferred.

After applying the coating liquid, the solvent is removed by heat treatment to obtain composite particles. The heat treatment temperature is usually set to about 150~250℃, especially 180~200℃. The gas environment for heat treatment is not limited, but it is ideally an inactive gas (non-oxidizing) gas environment such as nitrogen and argon. In addition, according to needs, for example, a series of steps consisting of a coating step and a heat treatment step may be further performed one or more times. This allows the coating amount to be appropriately controlled.

The surface of the composite particles obtained in this manner has a coating layer containing a polyfluoroalkyl methacrylate resin. By including the resin, it has excellent affinity with the inorganic oxide fine particles, so a tight coating layer with high adhesion can be formed on the surface of the particles, and higher water-repellency or oil-repellency can be exhibited.

The adhering amount of the composite particles (weight after drying) should be set to a sufficient amount required to form a three-dimensional network structure. It is usually set in the range of about 0.01~100g/ ^m2 , especially 0.1~20g/m2. m ² or so, preferably 0.5~10g/m ² , among which 0.6~5g/m ² is the best.

(2-2) Fluorine-containing resin The fluorine-containing resin will form a three-dimensional network structure together with the functional particles in the functional layer. Fluorine-containing resin is hydrophobic or oleophobic, so it easily repels moisture or moisture-rich materials. In addition, fluorine-containing resin can easily repel oil or oil-rich materials. Furthermore, in the present invention, the functional particles are joined to each other by the fluorine-containing resin, and the fluorine-containing resin and the functional particles form a three-dimensional network structure. By adopting such a structure, the water repellency and oil repellency become higher. In addition, it is preferable to bond the base material and the functional particles with a fluorine-containing resin so that the functional particles are supported (fixed) on the base material. Thereby, the functional layer is firmly fixed on the base material, and high durability can be obtained.

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. Examples include: polyfluoroalkyl methacrylate resin, polytetrafluoroethylene resin (PTFE), ethylene tetrafluoroethylene resin (ETFE), polydifluorovinylene resin, ethylene tetrafluoroethylene copolymer, perfluoroalkoxy At least one of alkane resin, tetrafluoroethylene and hexafluoropropylene copolymer, tetrafluoroethylene and perfluoroalkyl vinyl ether copolymer. The nature and state of these are not limited, and for example, aqueous dispersion type can be used appropriately.

In particular, in the present invention, a resin selected from the group consisting of polyfluoroalkyl methacrylate resin, polytetrafluoroethylene resin (PTFE), ethylene tetrafluoroethylene resin (ETFE), perfluoroalkoxyalkane resin and tetrafluoroethylene resin can be suitably used. At least one of the group consisting of vinyl fluoride and hexafluoropropylene copolymers. As these, well-known or commercially available ones can also be used.

Among these, the present invention preferably includes polyfluoroalkyl methacrylate resin as the fluorine-containing resin. In particular, when composite particles are used as functional particles, the functional layer contains a fluorine-containing resin and the fluorine-containing resin is substantially equivalent to the coating layer formed on the surface of the inorganic oxide fine particles, thereby improving the affinity between the functional particles and the fluorine-containing resin. The resistance will become higher, showing higher water-repellent durability and oil-repellent durability. The same resin as described above can be used, or a commercially available product can be used.

The adhering amount of the fluorine-containing resin (weight after drying) should be a sufficient amount to form a three-dimensional network structure. It is usually 0.5~30g/ ^m2 , and more preferably 0.5~5g/ ^m2. , where 2.5~5g/m ² is the best.

In addition, the ratio (weight ratio) between the functional particles (A) and the fluorine-containing resin (but excluding the fluorine-containing hydrophobic resin contained in the aforementioned functional particles) (B) in the three-dimensional network structure is as described above. For example, it can be set to A:B=20:1~1:50, or it can be set to A:B=20:1~1:30, but it is not limited to this. Therefore, for example, the weight ratio of functional particles (A): fluorine-containing resin (B) can also be set to about A: B = 1: 0.5~3.

(2-4)Other ingredients In the present invention, other components may be included in the functional layer (or three-dimensional network structure) within the scope that does not hinder the effects of the present invention. Examples include additives such as filling particles, coloring materials, dispersants, anti-settling agents, and defoaming agents. The total content of the additives in the functional layer can be, for example, about 50% by weight or less, or about 0 to 40% by weight, but is not limited to this.

In particular, filler particles can be suitably used in the present invention. By including filler particles to form inorganic oxide particles and nano microstructures, it can exhibit higher water repellency or oil repellency. As the filling particles, those with an average particle diameter D50 of 5 to 60 μm (preferably 10 to 30 μm) can be appropriately used. The material can be any of inorganic materials or organic materials, for example: polymethylmethacrylate (PMMA), styrene, low-density polyethylene (LDPE), high-density polyethylene (HDPE). ), at least one particle (powder) from the group consisting of acrylic resin, silicon oxide and alumina. When blending filler particles, the content is not limited. It is advisable to include filler particles at the following ratio: based on the weight after drying, the ratio of [fluorine-containing resin/(filler particles + fluorine-containing resin)] is 25 to 75% by weight. . When the ratio is less than 25% by weight, the fluororesin may not be able to sufficiently adhere the filling particles to the base material, and the filling particles may easily fall off. When the above ratio exceeds 75% by weight, for example, when the fluorine-containing resin without filled particles is 100% by weight, the desired oil-repellent durability or water-repellent durability can still be obtained.

2. Manufacturing method of laminated body The laminated body of the present invention can be appropriately produced by, for example, the first to third methods shown below.

The first method is a manufacturing method including the following steps: (1) a step of forming a coating film by applying a coating liquid to a substrate (coating film forming step), the coating liquid containing: (a) functional particles and (b) fluorine-containing resin, the (a) functional particles are at least one of (a1) composite particles and (a2) hydrophobic particles, and the (a1) composite particles contain methacrylic acid on the surface of the inorganic oxide fine particles. A coating layer of polyfluoroalkyl ester resin; and (2) a step of heat-treating the aforementioned coating film (heat treatment step) if necessary.

The second method is a manufacturing method including the following steps: (1) a step of forming a fluorine-containing coating film by applying a fluorine-containing coating liquid containing a fluorine-containing resin to a base material (fluorine-containing coating film forming step); ( 2) A step of forming a coating film containing functional particles by applying a coating liquid to the aforementioned fluorine-containing coating film (a step including composite particle coating film formation), the coating liquid including: (a1) composite particles and (a2) At least one functional particle of hydrophobic particles, and the (a1) composite particle has a coating layer containing polyfluoroalkyl methacrylate resin on the surface of the inorganic oxide microparticles; and (3) as required The step of subjecting the coating film obtained above to heat treatment (heat treatment step).

The third method is a manufacturing method including the following steps: (1) A step of forming a coating film containing functional particles by applying a coating liquid to a substrate (including a composite particle coating film forming step), the coating liquid containing (a1) At least one functional particle of composite particles and (a2) hydrophobic particles, and the (a1) composite particles are provided with a coating layer containing polyfluoroalkyl methacrylate resin on the surface of the inorganic oxide fine particles; (2) The step of obtaining a fluorine-containing coating film by applying a fluorine-containing coating liquid containing a fluorine-containing resin to the aforementioned functional particle-containing coating film (fluorine-containing coating film forming step); and (3) converting the aforementioned obtained coating film according to demand (3) The step of heat-treating the coating film (heat treatment step).

Among these, the second method may be more appropriately adopted. Thereby, a three-dimensional network structure can be constructed and reinforced while maintaining voids more reliably (that is, maintaining high oil repellency). The reason for this is not yet clear, but it is speculated that the functional particles arranged on the fluorine-containing coating absorb the fluorine-containing resin due to capillary action and become bridged. This can more effectively suppress or prevent the functional particles from falling off, resulting in excellent water-repellent durability or oil-repellent durability.

＜About method 1＞ Film formation steps In the coating film forming step, the coating film is formed by applying a coating liquid to the base material. The coating liquid contains: (a) functional particles and (b) fluorine-containing resin, the (a) functional particles are ( a1) At least one functional particle of composite particles and (a2) hydrophobic particles, and the (a1) composite particles are provided with a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of the inorganic oxide fine particles.

The coating liquid usually contains functional particles, fluorine-containing resin and solvent. The types of functional particles and fluorine-containing resin, the ratio of the two, etc. are preferably within the ranges described above.

In addition, the solvent is not limited and can be appropriately selected depending on the type of fluorine-containing resin used. It can be appropriately selected from the following organic solvents, for example: alcohol solvents (ethanol, methanol, isopropyl alcohol (IPA), hexanol, etc.), ketone solvents (acetone, ketone, methyl ethyl ketone (MEK) ), etc.), hydrocarbon solvents (cyclohexane, n-pentane, n-hexane, methylcyclohexane (MCH), etc.), aromatic solvents (toluene, etc.), glycol solvents (propylene glycol, hexylene glycol, etc.) , diethylene glycol monobutyl ether, 1,5-pentanediol, etc.).

The coating liquid may be a solution in which a fluorine-containing resin or the like is dissolved in a solvent, and is particularly preferably in the form of a dispersion in which functional particles and fluorine-containing resin particles are dispersed in a solvent. With this, when the coating liquid is applied to the base material, the functional particles and the fluororesin particles are uniformly coated. Therefore, while maintaining the characteristics of the functional particles, not only the adhesion between the functional particles is improved, but also the adhesion between the functional particles is improved. , and can also improve the adhesion between the functional layer and the substrate. Then, when the dispersion is applied to the base material, most of the functional particles and fluororesin particles will move downward (in the direction of gravity), so the void ratio in the area of the functional layer close to the base material becomes low, and the functional layer becomes more functional. The void ratio in the most surface side area of the layer becomes higher. This can effectively form a functional layer with a tilted structure.

The method of applying the coating liquid is not particularly limited, and examples of suitable methods include: roller coating, various gravure coatings, bar coaters, blade coatings, comma coaters, spray coating, brush coating, etc. A well-known method.

After coating, a drying step can also be implemented according to needs. The drying method is not particularly limited and may be either natural drying or heat drying. There is no limit to the heating temperature during heating and drying, but it is usually set to about 80~140℃, especially 100~120℃. The heating time should be set appropriately according to the heating temperature, etc. It can usually be set to about 3 to 60 seconds, but it is not limited to this.

Heat treatment steps In the present invention, a heat treatment step can be used to heat-treat the coating film obtained in the aforementioned coating film forming step according to needs. Through heat treatment, the functional particles and fluororesin in the functional layer will be more tightly bonded, and by bonding the fluororesin to the base material, a laminate with excellent adhesion between the base material and the functional layer can be obtained. body. Furthermore, during the heat treatment step, part of the functional particles and/or fluorine-containing resin can be embedded in the base material, thereby achieving higher adhesion and more effectively integrating the base material and the functional layer. structure.

The heat treatment temperature is ideally set to a temperature lower than the heat-resistant temperature of the base material, and is set to a temperature range from the minimum glass transition temperature to about the melting point of the fluorine-containing resin contained in the functional layer. Therefore, for example, if the heat-resistant temperature of the base material is 660°C, the glass transition temperature of the fluorine-containing resin is 100°C, and the melting point is 270°C, the heat treatment temperature can be set to about 100 to 270°C (for example, about 150 to 200°C).

In addition, the heat treatment time is preferably set to be a sufficient time required to obtain the desired adhesion, and may be set to about 10 seconds to 60 minutes, for example, but is not limited to this.

＜About the second method＞ Fluorine coating film formation steps In the fluorine-containing coating film forming step, the fluorine-containing coating film is formed by applying a fluorine-containing coating liquid containing a fluorine-containing resin to the base material.

The coating fluid usually contains fluorine-containing resin and solvent. The type of fluorine-containing resin, the ratio thereof, etc. can be set as described above. In addition, the same solvent as those exemplified in the first method can be used.

The coating liquid may be a solution in which a fluorine-containing resin is dissolved in a solvent, and is particularly preferably in the form of a dispersion in which fluorine-containing resin particles are dispersed in a solvent. Thereby, since the fluorine-containing resin particles are uniformly coated when the coating liquid is applied to the base film, the adhesion between the finally formed functional layer and the base material can be further improved.

The coating method is not particularly limited, and known methods such as roller coating, various gravure coatings, rod coaters, blade coatings, comma coaters, spray coating, and brush coating can be appropriately used. The coating amount can be set to ^about 0.1~60g/m2 based on dry weight, or it can also be set to 0.2~50g/ ^m2 , but is not subject to these restrictions.

After coating, a drying step can also be implemented according to needs. The drying method is not particularly limited and may be either natural drying or heat drying. There is no particular limit to the heating temperature during heating and drying, but it is usually set to about 80 to 140°C, and preferably 100 to 120°C. The heating time should be set appropriately according to the heating temperature, etc. It can usually be set to about 3 to 60 seconds, but it is not limited to this.

Steps for forming coating film containing functional particles In the step of forming a coating film containing functional particles, the coating film containing functional particles is formed by applying a coating liquid containing (a) functional particles to the fluorine-containing coating film, and the (a) functional particles are (a1) ) composite particles and (a2) hydrophobic particles, and the (a1) composite particles are provided with a coating layer containing polyfluoroalkyl methacrylate resin on the surface of the inorganic oxide fine particles.

The coating liquid usually contains functional particles and solvent. The types, production methods, etc. of the functional particles are as described above. Moreover, the solvent etc. can also use the same thing as those mentioned in the 1st method. The solid content concentration of the coating liquid can be set in the range of about 20 to 60% by weight, for example, but is not limited to this.

The coating liquid is preferably in the form of a dispersion in which functional particles are dispersed in a solvent. Thereby, when the coating liquid is applied to the fluorine-containing coating film, the functional particles are uniformly coated, so the adhesion between the finally formed functional layer and the base material can be further improved. Therefore, based on this point, when using composite particles as functional particles, it is desirable to use a solvent that does not dissolve the coating layer of the composite particles.

The method of applying the coating liquid is not particularly limited, and is preferably carried out in the same manner as the method of forming the fluorine-containing coating film. For example, known methods such as roller coating, various gravure coatings, bar coaters, blade coatings, comma coaters, spray coating, and brush coating can be appropriately used.

After coating, a drying step can also be implemented according to needs. The drying method is not particularly limited and may be either natural drying or heat drying. There is no limit to the heating temperature during heating and drying, but it is usually set to about 80~140℃, especially 100~120℃. The heating time should be set appropriately according to the heating temperature, etc. It can usually be set to about 3 to 60 seconds, but it is not limited to this.

Heat treatment steps In the present invention, the coating film obtained in the aforementioned coating film forming step (ie, the coating film including fluororesin and functional particles) can be further heat-treated according to the requirements. By performing heat treatment, the functional particles and the fluorine-containing resin in the porous functional layer will be bonded more tightly, and by bonding the fluorine-containing resin with the base material, close adhesion between the base material and the porous functional layer can be obtained. A laminate with excellent properties. Furthermore, during the heat treatment step, part of the functional particles and/or fluorine-containing resin can be embedded in the base material, thereby achieving higher adhesion and integrating the base material and the functional layer more effectively. structure.

The heat treatment temperature is ideally set to a temperature lower than the heat-resistant temperature of the base material, and is set to a temperature range from the minimum glass transition temperature to about the melting point of the fluorine-containing resin contained in the functional layer. Therefore, for example, if the heat-resistant temperature of the base material is 660°C, the glass transition temperature of the fluorine-containing resin is 100°C, and the melting point is 270°C, the heat treatment temperature can be set to about 100 to 270°C (especially about 150 to 220°C ).

In addition, the heat treatment time is preferably set to a sufficient time required to obtain the desired adhesion. For example, it can be set to about 10 seconds to 60 minutes, but is not limited to this.

＜About the third method＞ The third method can be implemented according to 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 changed.

3. Use of laminates The laminate of the present invention can be used in various applications, for example, applications requiring at least any one of anti-adhesion properties, antifouling properties, water repellency, oil repellency, and the like.

It can be suitably used as a packaging material or container for packaging or sealing food, medicine, cosmetics, etc., for example. The present invention can provide a packaging product, for example, a packaging product in which various contents are put into a packaging bag formed using the laminate of the present invention so that the functional layer is placed inside, and then sealed. [Example]

Examples and comparative examples are shown below and the characteristics of the present invention are explained more specifically. However, the scope of the present invention is not limited by the examples.

[Example 1] (1) A commercially available aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, soft aluminum foil, thickness 30 μm) was used as the fluorine-containing resin coating base material. Also, polyfluoroalkyl methacrylate resin (PFMA) (manufactured by AGC Inc., "AG-E060", water-based dispersion type with surface free energy 14 mJ/m ² and solid content 20 mass %) 100 for the fluorine-containing resin parts by weight, add 100 parts by weight of ethanol and stir thoroughly to prepare a coating liquid (dispersion). Use the above coating liquid and use a bar coater #14 to coat the surface of the above aluminum foil to a dry weight of 5.0g/ ^m2 , then heat it in an oven at 120°C for 40 seconds to evaporate the solvent to form Fluorine coating. (2) Formation of functional layer (2-1) Preparation of composite particles Hydrophilic silicon oxide particles (product name "AEROSIL 200", manufactured by Nippon Aerosil Co., Ltd., BET specific surface area 200m ² /g, average primary particle diameter 12nm) was placed into the reaction tank, and 500g of a commercially available surface treatment agent was sprayed while stirring in a nitrogen atmosphere, and then stirred at 200°C for 30 minutes and then cooled. Thereby, a powder composed of composite particles is obtained. In addition, the above-mentioned surface treatment agent uses polyfluorooctyl methacrylate, 2-N,N-diethylamine ethyl methacrylate, 2-hydroxyethyl methacrylate and 2,2'-ethylenedioxybis An aqueous dispersion of a copolymer of ethyl dimethacrylate (solid content concentration: 20% by mass) was used as the polyfluoroalkyl methacrylate resin (PFMA). (2-2) Preparation of a dispersion liquid containing composite particles. A dispersion liquid containing composite particles was prepared by adding and mixing 50 parts by weight of the obtained composite particles into 50 parts by weight of ethanol. (2-3) Coating of composite particle-containing dispersion The obtained composite particle-containing dispersion was applied on the aforementioned fluorine-containing coating film using a bar coater #8, and then dried at 120°C × 40 seconds. , thereby forming a functional layer. The coating amount of the composite particles in the functional layer was confirmed in advance by using a bar coater to coat other base materials under the same conditions so that the weight after drying reaches 2.0g/m ² . In this manner, a laminate in which an organic functional layer is formed on the surface of the base material is produced. Here, the manufacturing conditions and the like of Example 1 are also shown in Table 1. In addition, the manufacturing conditions, etc. of the following Examples and Comparative Examples are also shown in Table 1.

[Example 2] When forming a fluorine-containing coating film, a water-based polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC Inc.) with a surface free energy of 14 mJ/m ² and a solid content of 20% by mass was used. Dispersed type) 100 parts by weight, 20 parts by weight of PTFE powder ("TLP10F-1" manufactured by Chemours-Mitsui Fluoroproducts Co., Ltd.) and 100 parts by weight of ethanol were placed in a mixer ("Degassing Rentaro" manufactured by Thinky Corporation ARV-310") and mixed at 2000 rpm for 1 minute and 30 seconds to prepare a coating liquid, and then applied it with a rod coater #10. Except for this, the base material was produced in the same manner as in Example 1. A laminate with functional layers is formed on the surface.

[Example 3] When forming a fluorine-containing coating, a water-based polyfluoroalkyl methacrylate resin ("AGE-060" manufactured by AGC Inc.) with a surface free energy of 14 mJ/m ² and a solid content of 20% by mass was used. Dispersed type) 100 parts by weight, 20 parts by weight of filled particles (Mitsui Chemicals, Inc. "MIPELON (registered trademark) ("Defoaming Rentaro ARV-310" manufactured by Thinky Corporation) and mix at 2000 rpm for 1 minute and 30 seconds to prepare the coating liquid, and then apply it with the rod coater #10, otherwise, use the In the same manner as in Example 1, a laminate with an organic functional layer formed on the surface of the base material was produced.

[Example 4] When forming a fluorine-containing coating film, ethanol was added to 100 parts by weight of polytetrafluoroethylene ("TLP10F-1" manufactured by Chemours-Mitsui Fluoroproducts Co., Ltd., surface free energy: 5 mJ/m ² ) 100 parts by weight and stir thoroughly to prepare a coating liquid. The coating liquid was applied with a bar coater #14, and the composite particle dispersion was dried at 200° C. In this way, a laminate with an organic layer formed on the surface of the base material is produced.

[Example 5] When forming a fluorine-containing coating film, a water-based polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC Inc.) with a surface free energy of 14 mJ/m ² and a solid content of 20% by mass was used. Dispersed type) 100 parts by weight, add 200 parts by weight of ethanol and stir thoroughly to prepare a coating liquid. Use this coating liquid and use a bar coater #3 to apply the coating liquid to a weight of 0.5 g/ ^m2 after drying. Otherwise, the base material is produced in the same manner as in Example 1. A laminate with functional layers is formed on the surface.

[Example 6] When forming a fluorine-containing coating film, polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC Inc.) was coated with a rod coater #36, surface free energy 14 mJ/m ² , solid (a water-based dispersion type with an ingredient content of 20% by mass), after drying, the weight becomes 15g/ ^m2 , then dry it by heating it in an oven at 120°C for 60 seconds to evaporate the solvent, and repeat this operation two more times to dry it. The final weight reaches a total of 30g/ ^m2 to form a fluorine-containing coating. Next, use a rod coater #5 to apply the composite particle-containing dispersion so that the coating amount of the composite particles becomes 1.0g/m ² , and then dry it at 120°C × 40 seconds to form a functional layer. Otherwise, in the same manner as in Example 1, a laminate with an organic functional layer formed on the surface of the base material was produced.

[Example 7] The composite particle-containing dispersion was coated by bar coater #3 so that the coating amount of the dried composite particles was 0.5 g/m ² based on the weight after drying. Otherwise, In the same manner as in Example 1, a laminate in which an organic functional layer was formed on the surface of the base material was produced.

[Example 8] The composite particle-containing dispersion was coated with a bar coater #14 so that the coating amount of the dried composite particles was 5.0 g/m ² based on the dry weight. Otherwise, In the same manner as in Example 1, a laminate in which an organic functional layer was formed on the surface of the base material was produced.

[Example 9] When forming a fluorine-containing coating film, polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC Inc., surface free energy 14 mJ/m ² , solid) was coated with a rod coater #8 Aqueous dispersion type with an ingredient content of 20% by mass), so that the dried weight reaches 2.5g/m ² , and then dried by heating in an oven at 120°C for 40 seconds to form a fluorine-containing coating film. Next, the composite particle-containing dispersion is coated on the aforementioned fluorine-containing coating film using a bar coater #36, and dried at 120°C × 60 seconds, and then coated using a bar coater #36. , and after drying at 120°C × 60 seconds, further coating with a rod coater #20, and drying at 120°C × 60 seconds, so that the coating amount of the composite particles is based on the weight after drying. 50 g/m ² , except for this, in the same manner as in Example 1, a laminate in which an organic layer was formed on the surface of the base material was produced.

[Example 10] When forming a fluorine-containing coating film, a water-based polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC Inc.) with a surface free energy of 14 mJ/m ² and a solid content of 20% by mass was used. Dispersed type) 100 parts by weight, 180 parts by weight of filling particles ("TECHPOLYMER SBX-17" manufactured by Sekisui Kasei Co., Ltd., polystyrene beads, average particle diameter 17 μm) and 250 parts by weight of ethanol were placed in a mixer ( "Degassing Rentaro ARV-310" (manufactured by Thinky Corporation)) and mix at 2000 rpm for 1 minute and 30 seconds to prepare a coating liquid, and then apply it with a bar coater #3 so that the dry weight reaches 2.5 g/ m ² for coating, except that the same manner as in Example 1 was used to prepare a laminate in which an organic functional layer was formed on the surface of the base material.

[Example 11] When forming a fluorine-containing coating film, a water-based polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC Inc.) with a surface free energy of 14 mJ/m ² and a solid content of 20% by mass was used. Dispersed type) 100 parts by weight, 60 parts by weight of filled particles ("TECHPOLYMER SBX-17" manufactured by Sekisui Kasei Co., Ltd., polystyrene beads, average particle diameter 17 μm) and 120 parts by weight of ethanol were placed in a mixer ( "Degassing Rentaro ARV-310" (manufactured by Thinky Corporation)) was mixed at 2000 rpm for 1 minute and 30 seconds to prepare the coating liquid, and then applied with the rod coater #5. Otherwise, the same method as in the Example was used. 1 In the same manner, a laminate with an organic layer formed on the surface of the base material is produced.

[Example 12] When forming a fluorine-containing coating film, a water-based polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC Inc.) with a surface free energy of 14 mJ/m ² and a solid content of 20% by mass was used. Dispersed type) 100 parts by weight, 60 parts by weight of filled particles ("TECHPOLYMER MBX-20" manufactured by Sekisui Kasei Co., Ltd., polymethyl methacrylate resin (PMMA) beads, average particle diameter 20 μm), and 120 parts by weight of ethanol Put the parts by weight into a mixer ("Degassing Rentaro ARV-310" manufactured by Thinky Corporation) and mix at 2000 rpm for 1 minute and 30 seconds to prepare the coating liquid, and then apply with the bar coater #5, except for Except for this, in the same manner as in Example 1, a laminate with an organic functional layer formed on the surface of the base material was produced.

[Example 13] When forming a fluorine-containing coating, a water-based polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC Inc.) with a surface free energy of 14 mJ/m ² and a solid content of 20% by mass was used. Dispersed type) 100 parts by weight, 60 parts by weight of filler particles ("HS-103" manufactured by NIPPON STEEL Chemical & Material Co., Ltd., oxidized silicon spherical particles, average particle diameter 28 μm) and 120 parts by weight of ethanol were added and mixed ("Degassing Rentaro ARV-310" manufactured by Thinky Corporation) and mix at 2000 rpm for 1 minute and 30 seconds to prepare the coating liquid, and then apply it with the rod coater #5. Otherwise, use the In the same manner as in Example 1, a laminate with an organic functional layer formed on the surface of the base material was produced.

[Example 14] When forming a fluorine-containing coating film, 100 parts by weight of ethanol is added to 100 parts by weight of fluorine-containing resin ethylene tetrafluoroethylene (ETFE) ("Z8820X" manufactured by AGC Inc., in powder form) and stirred thoroughly to prepare a coating. Apply liquid. The coating liquid was applied with a bar coater #14, and the composite particle dispersion was dried at 200° C. In this way, a laminate with an organic layer formed on the surface of the base material is produced.

[Example 15] When forming a fluorine-containing coating film, filler particles ("TECHPOLYMER SBX-17" manufactured by Sekisui Kasei Co., Ltd., polyethylene) were added to 100 parts by weight of ethylene tetrafluoroethylene ("Z8820X" manufactured by AGC Inc., in powder form). 60 parts by weight of styrene beads (average particle diameter: 17 μm) and 120 parts by weight of ethanol were placed in a mixer ("Degassing Rentaro ARV-310" manufactured by Thinky Corporation) and mixed at 2000 rpm for 1 minute and 30 seconds to prepare and apply liquid, and then coated with the rod coater #5, and then dried at 200°C A laminate of organic layers is formed on the surface of the base material.

[Example 16] A CPP film with a thickness of 250 μm ("TAS-0125" manufactured by Taisei Kako Co., Ltd.) was used as the base material. In addition, when forming a fluorine-containing coating film, the polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC Inc., a water-based dispersion type with a surface free energy of 14 mJ/m ² and a solid content of 20% by mass) 100 parts by weight, 20 parts by weight of filling particles ("MIPELON (registered trademark) XM221U" manufactured by Mitsui Chemicals, Inc., polyethylene beads, average particle diameter 25 μm) and 120 parts by weight of ethanol were placed in a mixer (manufactured by Thinky Corporation) "Degassing Rentaro ARV-310") and mixed at 2000rpm for 1 minute and 30 seconds to prepare a coating liquid, and then applied it with a bar coater #10, except that it was in the same manner as in Example 1 , to produce a laminate in which an organic functional layer is formed on the surface of the base material.

[Example 17] A PET film with a thickness of 100 μm ("EMBLET SD" manufactured by UNITIKA, Ltd.) was used as the base material. In addition, when forming a fluorine-containing coating film, the polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC Inc., a water-based dispersion type with a surface free energy of 14 mJ/m ² and a solid content of 20% by mass) 100 parts by weight, 20 parts by weight of filling particles ("MIPELON (registered trademark) XM221U" manufactured by Mitsui Chemicals, Inc., polyethylene beads, average particle diameter 25 μm) and 120 parts by weight of ethanol were placed in a mixer (manufactured by Thinky Corporation) "Degassing Rentaro ARV-310") and mixed at 2000rpm for 1 minute and 30 seconds to prepare a coating liquid, and then applied it with a bar coater #10, except that it was in the same manner as in Example 1 , to produce a laminate in which an organic functional layer is formed on the surface of the base material.

[Example 18] A soft aluminum foil with a thickness of 20 μm (manufactured by Toyo Aluminum Co., Ltd., 1N30) was used, and a dispersion CPP coating agent (manufactured by T&K TOKA Co., Ltd. "heat seal" was applied with a rod coater #14 varnish PPX-16", solid content: 15% by mass), and then dried at 150°C for 60 seconds to a post-drying amount of 3 g/m ² to form a primer layer on the soft aluminum foil. When forming a fluorine-containing coating film, 100 weight of polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC Inc., water-based dispersion type with surface free energy of 14 mJ/m ² and solid content of 20% by mass) 20 parts by weight of filled particles ("MIPELON (registered trademark) Soak Rentaro ARV-310") and mix it for 1 minute and 30 seconds at 2000 rpm to prepare a coating liquid, and then apply it on the aforementioned primer layer with a rod coater #10. In addition, use the same In the same manner as in Example 1, a laminate with an organic functional layer formed on the surface of the base material was produced.

[Example 19] (1) A commercially available aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, soft aluminum foil, thickness 20 μm) was used as the fluorine-containing resin coating base material. Also, based on 100 parts by weight of fluorine-containing polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC Inc., water-based dispersion type with surface free energy of 14 mJ/m ² and solid content of 20% by mass), 100 parts by weight of ethanol was added and stirred thoroughly to prepare a coating liquid (dispersion). Use the above coating liquid and use a rod coater #5 to coat the surface of the above aluminum foil to a dry weight of 1.0g/ ^m2 , then heat it in an oven at 120°C for 40 seconds to evaporate the solvent. This forms a fluorine-containing coating film. (2) Preparation of a dispersion containing hydrophobic particles: 5 g of hydrophobic particles (product name "AEROSIL R812S" manufactured by Evonik Degussa Co., Ltd., BET specific surface area: 220 m ² /g, primary particle average particle size: 7 nm) Disperse in 100 mL of ethanol to prepare a hydrophobic particle-containing dispersion. (3) Coating of the hydrophobic particle-containing dispersion. The obtained hydrophobic particle-containing dispersion is applied on the aforementioned fluorine-containing coating film using a bar coater #8, and then dried at 120°C × 40 seconds. This forms a functional layer. The coating amount of hydrophobic particles in the functional layer is confirmed in advance by using a bar coater to coat other base materials under the same conditions so that the weight after drying reaches 2.0g/m ² . In this manner, a laminate in which an organic functional layer is formed on the surface of the base material is produced.

[Example 20] The fluorine-containing coating film produced by the same method as Example 19 was coated with a rod coater #24 so that the hydrophobic particles reached 10.0 g/m ² in terms of dry weight, and then Dry at 120°C x 90 seconds to form a functional layer.

[Example 21] The fluorine-containing coating film produced by the same method as Example 19 was coated with the rod coater #24 so that the hydrophobic particles reached 50.0g/m ² in weight after drying, and Dry under the conditions of 120°C × 90 seconds, and repeat the above-mentioned coating and drying 5 times to form a functional layer.

[Example 22] A commercially available aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, soft aluminum foil, thickness 20 μm) was used as the base material. In addition, use the coating liquid adjusted in Example 19 and apply it to the surface of the above-mentioned aluminum foil using a rod coater #24, so that the weight after drying reaches 15.0g/ ^m2 , and then heat it in an oven at 120°C for 40 Seconds, repeat the above operation again, thereby forming a fluorine-containing coating film with a dry weight of 30.0g/ ^m2 . Next, use the coating liquid of Example 19 (2) and apply it on the aforementioned fluorine-containing coating film by a bar coater 16, so that the hydrophobic particles reach 5.0 g/ ^m2 in weight after drying, and then apply the coating liquid at 120°C Dry under conditions of ×90 seconds to form a functional layer.

[Comparative example 1] A laminate was produced in the same manner as in Example 1 except that the base material was not coated with the fluororesin-containing coating liquid but only the composite particle-containing dispersion liquid.

[Comparative example 2] A laminated body was produced in the same manner as in Example 1 except that the base material was coated with a fluororesin-containing coating liquid and the composite particle-containing dispersion liquid was not applied.

[Comparative Example 3] When forming a fluorine-containing coating film, polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC Inc.) was coated with a bar coater #36, surface free energy 14 mJ/m ² , solid (water-based dispersion type with an ingredient content of 20% by mass), and after drying the weight reaches 15g/ ^m2 , heat it in an oven at 120°C for 60 seconds to dry it and evaporate the solvent. Repeat this operation two more times until the The total weight after drying is 30g/m ² . Next, dilute the composite particle dispersion with ethanol, and apply it with a bar coater #3 so that the weight of the composite particles after drying reaches 0.2g/m ² , and then dry at 120°C × 40 seconds to form Except for the functional layer, a laminated body was produced in the same manner as in Example 1.

[Comparative Example 4] When forming a fluorine-containing coating film, a water-based polyfluoroalkyl methacrylate resin ("AG-E060" manufactured by AGC Inc.) with a surface free energy of 14 mJ/m ² and a solid content of 20 mass % was used. dispersion type) and 100 parts by weight of ethanol to prepare a coating liquid. Use this coating liquid and apply it with a bar coater #3 until the weight after drying reaches 0.2g/ ^m2 , and then heat it in an oven at 120°C for 40 seconds to dry it. Next, the composite particle dispersion is coated with a bar coater #36 and dried at 120°C x 60 seconds, and then coated with a bar coater #36 and dried at 120°C x 60 seconds. , further coated by rod coater #20, and ^dried under the conditions of 120°C Make the laminated body in the same way.

[Comparative Example 5] Maleic anhydride-modified polyolefin resin (MAPO) (290628-2 manufactured by Tanaka Chemical Industries, Ltd., surface energy 30 mJ/m ² , solid content 20 mass %) was used as the coating liquid instead of the fluorine-containing resin. Use, except that the laminated body was produced by the same method as Example 1.

[Comparative Example 6] In terms of coating of substituted fluorine-containing resin, compared to maleic anhydride-modified polyolefin resin (MAPO) (290628-2 manufactured by Tanaka chemical industries, Ltd., surface energy 30 mJ/m ² , solid content 20 mass %) 100 parts by weight of filling particles (Mitsui Chemicals, Inc. "MIPELON (registered trademark) XM221U", polyethylene beads, average particle diameter 25 μm) 20 parts by weight and 120 parts by weight of IPA were placed in a mixer "Degassing Rentaro ARV-310" manufactured by Thinky Corporation) and mixed at 2000rpm for 1 minute and 30 seconds to prepare the coating liquid, and then applied it with the rod coater #10. Otherwise, the same as in the Example 1Make the laminate in the same way.

[Comparative Example 7] Styrene butadiene rubber-based resin (SBR) ("DYNARON 1320P" manufactured by JSR Corporation) was dissolved in toluene instead of fluorine-containing resin. It was used as a coating liquid with a solid content of 10% by mass, and was used with a bar coater. No. 20 was applied, except that the laminated body was produced by the same method as Example 1.

[Comparative example 8] Acrylic modified polyolefin resin (APO) (300214-1 manufactured by Tanaka Chemical Industries, Ltd., solid content 20% by mass) was used as the coating liquid instead of the fluorine-containing resin. In addition, the same method as in Example 1 was used. Make the laminated body in the same way.

[Comparative Example 9] The base material is a CPP film with a thickness of 50 μm ("P1011" manufactured by Toyobo Co., Ltd.), and acrylic modified polyolefin resin (APO) (300214-1 manufactured by Tanaka Chemical Industries, Ltd., solid content 20 mass%) is used instead of fluorine-containing resin Except using it as a coating liquid, the laminated body was produced by the same method as Example 1.

[Comparative Example 10] A laminate was produced in the same manner as in Example 19 except that the base material was not coated with a fluorine-containing resin coating liquid and only the hydrophobic particle-containing dispersion liquid was coated.

[Comparative Example 11] Acrylic modified polyolefin resin (APO) (300214-1 manufactured by Tanaka Chemical Industries, Ltd., solid content 20% by mass) was used as the coating liquid instead of the fluorine-containing resin coating liquid. A laminated body was produced in the same manner as in Example 19.

[Comparative Example 12] A commercially available aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, soft aluminum foil, thickness 20 μm) was used as the base material. In addition, acrylic modified polyolefin resin (APO) (300214-1 manufactured by Tanaka Chemical Industries, Ltd., solid content 20% by mass) was diluted with IPA to prepare a coating liquid with a solid content of 5% by mass, and a rod coater was used. #3 is applied on the aforementioned aluminum foil to a weight of 0.1g/m ² after drying. Next, use the coating liquid of Example 19 (2) and apply it on the above-mentioned APO coating film with a bar coater #26, so that the hydrophobic particles reach 12.5g/m ² in weight after drying, and then use Dry under the conditions of 120°C × 90 seconds. By repeating the above operation twice, the weight of the hydrophobic particles after drying reaches 25.0g/m ² to form a functional layer.

[Test Example 1] (Cross-sectional observation) The obtained laminated body was embedded in epoxy resin and cut into cross sections, and then the cut base material cross sections were irradiated with Ar ion beams using an ion milling device (IB-19520CCP manufactured by JEOL Co., Ltd.) to produce Smooth section. Next, using a scanning electron microscope ("SU8020" manufactured by Hitachi High-Technologies Corporation), the formation of a three-dimensional network structure in which the composite particles were bridged by the fluorine-containing resin was confirmed at any place in a plan view. As this observation example, a cross-sectional image of the laminated body of Example 1 is shown in FIG. 2 , and a cross-sectional image of the laminated body of Comparative Example 1 is shown in FIG. 3 . As a result of the observation, the case where the three-dimensional network structure in which the functional particles were bridged with the fluorine-containing resin was formed was evaluated as "○", and the case where the three-dimensional network structure was not formed was evaluated as "×". Therefore, for example, the case where the fluorine-containing resin is not bridged and a three-dimensional network structure is formed of only functional particles is regarded as "×".

[Test Example 2] (Measurement of specific surface area) According to the static volume method stipulated in Japanese Industrial Standard JIS Z8830:2013, using a specific surface area measuring device NOVA 1000e manufactured by Quantachrome Instruments Incorporation, each laminated body sample was measured in the following manner Determine the specific surface area. The results are shown in Table 2. (1) Filling method of laminated body The sample is made by cutting a laminated body of 100 mm long x 100 mm wide into a width of 10 mm and filling it in a predetermined glass tube. At this time, cut and fill while being careful not to let the functional layer fall off. (2) Pre-processing of the laminate The above-mentioned sample was pre-processed at 100° C. for 1 hour under vacuum using the above-mentioned specific surface area measuring device, and gases such as water vapor were degassed in advance. (3) Measurement of specific surface area of laminate The adsorption isotherm of the laminate was prepared using the following conditions. ･Adsorption gas: high-purity compressed nitrogen (Air Water West Japan Inc., manufactured by Amagasaki Factory Co., Ltd., purity 99.999% or above) ･Adsorption temperature: 77.35K ･Pressure tolerance: 0.100mmHg/0.100mmHg (adsorption/desorption) ･Equilibrium time: 60 seconds/60 seconds (adsorption/desorption) ･Equilibrium timeout: 240 seconds/240 seconds (adsorption/desorption) ･Measurement range: 0.05＜Relative pressure P/P0＜0.3 ･Thermal Delay (thermal delay time) : 180 seconds･Evacuation Cross-over Pressure: 20mmHg From the obtained adsorption isotherm of the laminated body, calculate the specific surface area of the laminated body using the BET multi-point method. At this time, the conditions are set as follows: the Correction Coefficient (correction coefficient) r, which indicates the accuracy of the obtained adsorption isotherm, is a value of 0.9999 or more and the number of points in the measurement chart (plot) is 4 or more; even if it is less than 4 When the number of points in the measurement chart is less than 0.9999, add one point at a time to the sample and repeat the calculation until r reaches a value above 0.9999. (4) The specific surface area of the functional layer is calculated from the obtained specific surface area St (m ² /g) of the laminate. The specific surface area S (m ² /g) of the functional layer formed on the surface of the base material can be calculated from "S=St/ (W1/Wt)" is calculated. 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 "the weight of the laminate - the weight of the base material." In this manner, the specific surface area of the functional layer is calculated. The results are shown in Table 2.

[Test Example 3] (Measurement of void ratio) The base material was embedded in epoxy resin, cut into cross sections, and then polished using an ion milling device ("IB-19520CCP" manufactured by JEOL Co., Ltd.). The cut base material cross-section is irradiated with Ar ion beam to create a smooth cross-section. Next, a scanning electron microscope ("SU8020" manufactured by Hitachi High-Technologies Corporation) was used to observe the sample cross-section under the conditions of electron emission current 4300nA, operating distance 3.0mm, and magnification 30000 times, and a secondary electron image with a field of view of 12 μm ² was obtained . In addition, when shooting secondary electronic images, the most appropriate focus is used in a way that does not produce astigmatism, and the brightness and contrast are adjusted to the most appropriate appearance in a way that does not cause clipping phenomena such as overexposure. . In addition, the sample was charged by using an electron beam and vapor-deposited appropriately using a vapor deposition device (JFC-1600 manufactured by JEOL Co., Ltd.) so that the image would not be blurred, and then observed. When taking images, the inventor envisions using image processing software to process them appropriately and adjust the position of the sample so that the entire field of view can reflect the functional layer. In addition, the area from the bottom of the functional layer to 50% of the thickness is defined as the "bottom", and the area from the bottom of the functional layer that exceeds 50% of the thickness to the surface of the functional layer is defined as the "upper". Then, the image processing software "WinROOF2018ver4.25" was used to binarize the secondary electronic image obtained, and the total number of pixels in the three-dimensional network structure part of the secondary electronic image was measured. The void ratio is calculated using "100% - (Binary ratio of the three-dimensional network structure part (%))". In addition, binarization is performed by using the automatic binarization system of the aforementioned software, selecting bright areas in the captured area, and then using the discriminant analysis method. In addition, the threshold value is based on the automatic binarization system and has not been changed. In this manner, the void ratio is calculated from the ratio of the total number of pixels in the three-dimensional network structure portion to the total number of pixels per 12 μm ² of the visual field range. The results are shown in Table 2. In addition, this operation was repeated 20 times on the bottom and top respectively, and the average value was taken as the void ratio. As an example, the binarized image of Example 1 is shown in FIG. 4 .

[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. The test specimens were coated specimens using the fluororesin before applying the functional particle dispersion liquid in the Examples and Comparative Examples. Place the test sample flatly on the stage of the contact angle meter with the fluororesin-coated side facing upward. Apply the Owens-Wendt theory, use pure water and diiodomethane as the probe liquid, and drop 1 microliter of the contact angle for 10 seconds from the side of the fluorine-containing resin, using the KYOWA interFAce Measurement and Analysis System FAMAS The software calculates it automatically. Repeat this method 3 times and take the average value. The surface free energy of the fluorine-containing resin in each example and comparative example was also measured in the same way. The results are shown in Table 2.

[Test Example 5] (Oil-repellent durability･Water-repellent durability) (1) Oil-repellent durability Commercially available edible oil with a known surface tension (Nisshin Zero Cholesterol Salad Oil manufactured by The Nisshin OilliO Group, Ltd., Surface tension 32mJ/m ² ) 80mL was placed into a 100mL glass bottle. Next, the glass bottle was placed in a heating stirrer, a stirrer was inserted, and the mixture was stirred at a speed of 50 rpm until it stabilized to 90°C. After that, a 20 mm × 20 mm sample was picked up with a clamp and immersed in the above-mentioned 90°C edible oil. At this time, adjust the position of the sample so that it does not contact the stirring bar. Take out the sample 2 hours after immersion, drop commercial olive oil with known surface tension (surface tension 32mJ/m ² ) onto the surface of the functional layer, and confirm the state of the droplets. Specifically, 1 mL of olive oil was dropped while tilting the test surface upward at an angle of 20 degrees or 45 degrees, and the following marks were used for evaluation: If the dripped olive oil still rolled even when tilted at 20 degrees, it was marked as "◎ ”. If the dripping olive oil does not completely roll when tilted at 20 degrees but all of the dripped olive oil rolls when tilted at 45 degrees, it is marked as “0”. When tilted at 45 degrees, part of the dripped olive oil rolls is marked as “△”. When tilted at 45 degrees, the dripping olive oil is marked as “△”. If the dripping olive oil is not rolled at all, it will be marked as "×". The results are shown in Table 2. Another method is to heat the edible oil placed in the above-mentioned glass bottle to 100°C and immerse the sample in the edible oil. Take out the sample 1 hour after immersion, then drop commercially available olive oil with known surface tension (surface tension 32mJ/m ² ) onto the surface of the functional layer, and confirm the state of the droplets. The evaluation method at this time was evaluated by marking "◎", "〇", "△", and "×" in the same manner as in the case of 90° C. × 2 hours. The results are shown in Table 2. (2) Water-repellent durability Place 80 mL of distilled water into a 100 mL glass bottle. Next, the glass bottle was placed in a heating stirrer, a stirrer was inserted, and the mixture was stirred at a speed of 50 rpm until it stabilized to 80°C. After that, a 20 mm × 20 mm sample was clamped with a clamp, and then immersed in the above-mentioned 80°C hot water. At this time, adjust the position of the sample so that it does not contact the stirring bar. Take out the sample 30 minutes after immersion, drop ion-exchange water (surface tension 72mJ/m ² ) onto the surface of the functional layer, and confirm the state of the droplets. Specifically, the test surface is tilted upward at an angle of 20 degrees or 45 degrees, and 1 mL of water is dropped, and the following marks are used for evaluation: If all the dropped water drops still roll even when tilted at 20 degrees, the mark is "◎". When tilted at 20 degrees, all the water droplets did not roll, but when tilted at 45 degrees, all the water droplets dropped were marked as "0". When tilted at 45 degrees, part of the water droplets rolled was marked as "△". When tilted at 45 degrees, the water droplets dropped completely. Those that are not rolled are marked with "×". The results are shown in Table 2.

[Table 1]

[Table 2]

It is clear from the results in Table 2 that the laminates of Examples 1 to 18 using composite particles can maintain good oil repellency even when immersed in high-temperature oil. Therefore, it is expected that high oil repellency can be exerted even when oil adheres to the functional layer due to long-term use of the laminate, or even when the functional layer is immersed in oil.

In particular, it can be seen that in the examples, the difference in surface free energy of fluorine-containing resin is larger than that of edible oil, which is 32 mJ/m ² . Therefore, among those with a specific surface area close to the value of only inorganic oxide fine particles, the functional particles and those containing The effect is particularly significant when the ratio of fluororesin is 1:3~4:1 by weight.

It was also found that the laminates of Examples 19 to 22 using hydrophobic particles can maintain good water repellency even when immersed in hot water.

10: Laminated body 11:Substrate 12:Functional layer 12a: Three-dimensional network structure 12b:gap A:Functional particles B: Fluorine-containing hydrophobic resin

FIG. 1 is a schematic diagram showing an example of the layer structure of the laminated body of the present invention. Figure 2 is a cross-sectional image of the laminated body of Example 1. Figure 3 is a cross-sectional image of the laminated body of Comparative Example 1. Figure 4 is a binarized image of Embodiment 1. Figure 4A is a cross-sectional image of a laminate showing a secondary electron image of an electron microscope; Figure 4B is a binarized image of Figure 4A; Figure 4C is about Figure 4A, using the automatic binarization system to select bright areas in the capture area After the area, the results of the discriminant analysis method are implemented.

10: Laminated body

11:Substrate

12:Functional layer

12a: Three-dimensional network structure

12b:gap

A:Functional particles

B: Fluorine-containing hydrophobic resin

Claims (11)

A laminated body including a base material and a functional layer, characterized by: (1) The functional layer contains a three-dimensional network structure; and (2) The three-dimensional network structure includes: (a) functional particles and (b) fluorine-containing hydrophobic resin, and the (a) functional particles are at least one of (a1) composite particles and (a2) hydrophobic particles, Furthermore, the composite particles (a1) are provided with a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of the inorganic oxide fine particles. The laminate according to claim 1, wherein the functional particles are fixed in the three-dimensional network structure by a fluorine-containing hydrophobic resin. The laminated body according to claim 1, wherein the functional layer is supported on the base material by bonding the base material and the functional particles with a fluorine-containing hydrophobic resin. For example, in the laminated body of claim 1, the specific surface area of the functional layer is ² ~195m2/g. For example, the laminated body of claim 1, wherein in the functional layer, the void ratio in the area from the bottom of the functional layer to 50% of the thickness is 0 to 45%, and, from the bottom of the functional layer exceeding 50% of the thickness to the surface of the functional layer ( The void ratio of the most surface area is 10~55%. The laminated body of claim 1, wherein the ratio of functional particles to fluorine-containing hydrophobic resin (excluding the fluorine-containing hydrophobic resin contained in the aforementioned functional particles) is 1:50~20 based on the solid content weight ratio. :1. The laminated body 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. The laminated body of claim 1, wherein the base material is at least one selected from the group consisting of metal foil, metal plate, resin film, resin board, paper, wood board, non-woven fabric or primer coatings thereof. species. The laminate of claim 1, wherein the average primary particle size of the inorganic oxide particles is 5 to 50 nm. The laminate of claim 1, wherein the three-dimensional network structure further contains filling particles with an average particle size D50 of 5 to 60 μm. A method for manufacturing a laminated body, which is a method for manufacturing a laminated body including a base material and a functional layer, and is characterized by comprising: (1) The step of forming a fluorine-containing coating film, which is performed by applying a fluorine-containing coating liquid containing a fluorine-containing hydrophobic resin to the substrate; and (2) The step of forming a composite particle-containing coating film is carried out by applying a coating liquid containing (a) functional particles composited with (a1) to the fluorine-containing coating film. At least one of particles and (a2) hydrophobic particles, and the (a1) composite particles are provided with a coating layer containing polyfluoroalkyl methacrylate resin on the surface of the inorganic oxide fine particles.