TW202328504A - Laminated body - Google Patents

Abstract

An object of the present invention is to provide a laminated body that can exhibit higher water-repellency and oil-repellency even in a severe condition or long-term using condition. The present invention is directed to a laminated body comprising (a) a base layer, (b) a primer layer, and (c) fine particles having water repellency and/or oil repellency fixed inside and/or on the primer layer, (1) the primer layer contains an adhesive resin; (2) part or all of the adhesive resin is a thermosetting resin, (3) the thermosetting resin is contained in the primer layer in an amount of 5 to 100% by mass; and (4) part or all of the fine particle group forms a functional layer having a three-dimensional network structure, and part or all of the fine particle group is exposed on the outermost surface of the laminated body.

Description

laminate

field of invention The present invention relates to a novel laminate, especially a water-repellent and/or oil-repellent laminate.

Background technique So far, water-repellent technology or oil-repellent technology has been extensively studied for the purpose of preventing adhesion of water, oil, food, and other materials. Especially in the fields of food, drink, pharmaceuticals, cosmetics, etc., for the purpose of suppressing or preventing the contents from adhering to packaging materials, products (materials) that have been subjected to water-repellent treatment or oil-repellent treatment have been continuously developed. Such water repellency and oil repellency can be imparted by modification of chemical properties by coating or physical properties by formation of fine unevenness.

For example, Patent Document 1 discloses a packaging material with water-repellent properties, which is sequentially laminated with a base material, a heat-sealing layer made of thermoplastic resin such as ethylene-vinyl acetate copolymer resin (EVA), polyolefin resin, etc. , Hydrophobic particles.

Also, Patent Document 2 discloses an antifouling sheet with oil-repelling properties, which sequentially includes a base material, a base layer made of thermoplastic resin, and oxide composite particles coated with polyfluoroalkyl methacrylate resin. layer body.

prior art literature patent documents Patent Document 1: Japanese Patent Laid-Open No. 2019-011085 Patent Document 2: Japanese Patent Laid-Open No. 2017-119353

Summary of the invention The problem to be solved by the invention However, in conventional technologies such as Patent Document 1 and Patent Document 2, although the desired water-repellent or oil-repellent properties can be obtained at the initial stage, if they are exposed to friction between articles, friction caused by fingers, etc., the water-repellent particles or The oil-repellent particles fall off and gradually become unable to obtain water-repellent or oil-repellent properties. That is, in the conventional technology, it is difficult to maintain water repellency or oil repellency under severe conditions or long-term use conditions.

Therefore, the main purpose of the present invention is to provide a laminate that can exhibit excellent water repellency or oil repellency even under severe use conditions or long-term use conditions.

means to solve problems In view of the problems of the conventional technology, the inventors have made careful studies and found that the above object can be achieved by a laminate having a specific layer structure, and thus completed the present invention.

That is, the present invention relates to the following laminate. 1. A laminate, characterized in that it comprises: a) a substrate layer; b) a primer layer; and c) a group of water-repellent and/or oil-repellent microparticles fixed inside and/or within the aforementioned primer layer and (1) the primer layer contains an adhesive resin; (2) part or all of the adhesive resin is a thermosetting resin; (3) the thermosetting resin contains 5 to 100% by mass in the primer layer; (4) Part or all of the above-mentioned microparticle group forms a functional layer having a three-dimensional network structure, and part or all of the above-mentioned microparticle group is exposed on the outermost surface of the laminate. 2. The laminate according to item 1 above, wherein the group of particles is exposed so as to cover substantially all of the outermost surface of the laminate. 3. The laminate according to item 1 above, wherein the adhesive resin is present in at least a part of gaps between fine particles of the fine particle group constituting the functional layer. 4. The laminate according to item 1 above, wherein the weight ratio [A/(A+B)] of the adhesive resin to the total amount of the adhesive resin (A) and the functional particles (B) is 5 to 97% . 5. The laminate according to item 1 above, wherein the primer layer further contains filler particles having an average particle diameter of 0.5 to 100 μm. 6. The laminate according to item 1 above, wherein the formed amount of the primer layer is 0.5 to 100 g/m ² in terms of the solid content of the adhesive resin. 7. The laminate according to item 1 above, wherein the formation amount of the aforementioned microparticle group is 0.01 to 100 g/m ² . 8. The laminate according to item 1 above, wherein the microparticle group is at least one of the following: (a) Composite particles comprising polyfluoroalkylmethyl groups on the surface of oxide particles with an average primary particle diameter of 5 to 50 nm. A resin coating layer of acrylate resin; and (b) hydrophobic oxide particles with an average primary particle diameter of 3-100 nm. 9. A method for manufacturing a laminate, which is a method of manufacturing a laminate, and the laminate comprises: a) a substrate layer; b) a primer layer; and c) a group of microparticles with water repellency and/or oil repellency, which is fixed on the inside and/or surface of the aforementioned primer layer; and the method of manufacturing the laminate is characterized in that it includes the following steps: (A) coating the substrate layer with a primer layer-forming coating comprising a thermosetting resin liquid and drying; and the step of coating a dispersion liquid containing water-repellent and/or oil-repellent microparticle groups on the coating film of the aforementioned coating liquid; or (B) coating the substrate layer with A step of forming a coating solution for forming a primer layer of water-based and/or oil-repellent fine particles and a thermosetting resin.

Invention effect According to the present invention, it is possible to provide a laminate that exhibits excellent water repellency or oil repellency even under severe use conditions or long-term use conditions.

For example, as in the first form described later, by having a specific layer structure of a) base material layer, b) primer layer, and c) functional layer, the base material layer and the functional layer can be firmly bonded by thermosetting resin . At the same time, on the side of the functional layer that is in contact with the primer layer, at least a part of the microparticles in the functional layer are firmly bonded to the thermosetting resin in the primer layer, and on the other hand, the surface side of the functional layer is There are groups of microparticles formed into a three-dimensional mesh structure, thereby existing in a state of maintaining gaps, so that water-repellent and/or oil-repellent properties can be exhibited. By firmly bonding (fixing) part or all of the fine particle group to the primer layer, the fine particle group becomes less likely to fall off, resulting in a laminate excellent in water-repellent or oil-repellent durability.

For another example, as in the second aspect described later, the base layer and the functional layer can be bonded more firmly by the thermosetting resin by setting the layer structure as if part of the fine particle group is included in the primer layer. That is, it is also possible to form a layer in which the microparticle group and the primer component are kneaded. At the same time, on the surface of the functional layer that is in contact with the substrate layer, at least a part of the microparticles in the functional layer will be firmly bonded to the substrate by using the thermosetting resin in the primer layer. On the surface side of the layer, groups of microparticles are formed into a three-dimensional mesh structure, thereby existing in a state of maintaining gaps, so that water and/or oil repellency can be exhibited. The aforementioned microparticle groups can be firmly bonded (fixed) by the primer layer, whereby the functional layer becomes less likely to fall off, resulting in a laminate having excellent water-repellent or oil-repellent durability.

A laminate having such characteristics can be suitably used, for example, as a packaging material. In particular, packaging materials are represented by lid materials, and can be suitably used for bags such as molded containers, wrapping paper, trays, pipes, bags, and pouches, for example. In the case of these uses, the bag body may be configured so that a functional layer is disposed on the side contacting the contents to be packaged.

When used as a packaging material, its contents may include water-based and/or oil-based liquids. That is, it can be applied to fluid contents. More specifically, in addition to food such as curry, stew, yogurt, fudge, pudding, seasoning (such as barbecue seasoning, sauce, etc.), liquid lotion, toothpaste, cleansing cream, cleansing mousse Cosmetics, pharmaceuticals, etc. are useful as packaging materials for storing the above-mentioned various contents.

form for carrying out the invention The laminate of the present invention is characterized in that it comprises: a) a substrate layer; b) a primer layer; and c) a group of water-repellent and/or oil-repellent microparticles fixed on the inside and/or surface of the primer layer on; and (1) The primer layer contains an adhesive resin; (2) Part or all of the adhesive resin is a thermosetting resin; (3) The thermosetting resin contains 5 to 100% by mass in the primer layer; (4) Part or all of the above-mentioned microparticle group forms a functional layer having a three-dimensional network structure, and part or all of the above-mentioned microparticle group is exposed on the outermost surface of the laminate.

Fig. 1 to Fig. 3 show an example of layer structure of an embodiment of the laminate of the present invention. In addition, in this specification, unless otherwise stated in advance, the group of microparticles having water repellency and/or oil repellency will be referred to as "functional particles".

The laminate 10 shown in FIG. 1 is a primer layer 12 laminated on the substrate layer 11, and a microparticle group 13a having water repellency and/or oil repellency is fixed on the primer layer (hereinafter, unless otherwise stated in advance) , also referred to as "functional particle") (this form is referred to as "the first form"). In this case, as shown in FIG. 1 , the functional particles 13a form the functional layer 13 having a three-dimensional network structure by mutual fixation (aggregation). A plurality of functional particles may form a functional layer as a whole, but a part of the functional particles may form a functional layer as long as the effect of the present invention is not hindered.

According to this, the laminated body 10 of the 1st form has the structure which has the base material layer 11, the primer layer 12 containing an adhesive resin, and the functional layer 13 in this order. Also, since the functional layer 13 is disposed as the outermost layer of the laminate, the functional layer is not substantially embedded in the primer layer, but substantially all of the functional layer is exposed to the outside.

However, the functional particles may be partially embedded in the primer layer within the range that does not hinder the effect of the present invention. For example, as in the functional particles 13a', only the lower part of one functional particle may sink into the primer layer.

In the functional layer 13, the gap formed between the plurality of functional particles 13a becomes a space (air layer) and becomes a porous layer. In the first aspect, the functional particles are preferably fixed to each other by cohesive force rather than passing through the bonding component. The functional particles can also be fixed through the adhesive component within the range that does not hinder the effect of the present invention.

In addition, the functional particles 13a in contact with the primer layer 12 are firmly fixed by the strong adhesive force of the primer layer 12 . As a result, the functional layer 13 is firmly fixed to the base material layer 11 through the primer layer 12 (especially thermosetting resin).

The laminate of the present invention may also include other layers within the range that does not hinder the effect of the present invention, but the above-mentioned substrate layer 11, primer layer 12 and functional layer 13 are preferably laminated in such a way that they are directly connected to each other.

The primer layer 12 may also include filler particles (not shown). That is, the present invention includes both a primer layer containing filled particles and a primer layer not containing filled particles as primer layers. When the filler particles are included, unevenness derived from the shape of the filler particles can be formed on the surface of the primer layer, thereby achieving higher durability. Regarding this point, filler particles (not shown) may also be contained in the primer layer 12 in the form of FIG. 2 described below.

As another embodiment of the laminate of the present invention, the following form is also included: as in the laminate 10 shown in FIG. on the paint layer 12 (this form is also referred to as "the second form"). Here, "present in the primer layer" means (i) a state where one functional particle 13a is completely embedded in the primer layer; and (ii) a part of one functional particle 13a is partially embedded in the primer The state in the layer both.

In the case of the second form, the functional particles 13a form a functional layer with a three-dimensional mesh structure by mutual fixation, but the functional layer on the primer layer side (below) exists in the primer layer, which is opposite to the primer layer. The side (upper) functional layer or the functional particles constituting it are exposed to the outside. That is, the functional layer 13 is arranged as the outermost layer of the laminate, but a part of the functional layer is embedded in the primer layer, and the remaining functional layer or functional particles are exposed to the outside. Therefore, the exposed portion may be substantially the entirety of the three-dimensional network structure exposed, and for example, as shown in Figure 3, the three-dimensional network structure is not exposed as a whole, but the functional particles 13a that constitute a part of it are in a state of being scattered or scattered on the surface (such as the form of discontinuous existence), this form is also included in the present invention. In this case, the area ratio of the functional particles occupying the entire surface of the laminate when the laminate is viewed from the vertical upper side of the functional layer can be, for example, in the range of about 10 to 90% according to the desired water repellency or repellency The oiliness is properly set, but not limited to this.

In the second form, part or all of the functional particles 13a also form a functional layer having a three-dimensional network structure. In the functional layer 13, the gaps formed by a plurality of functional particles may be spaces, and may be filled with components (especially adhesive resin) constituting the primer layer. Especially for the portion where the functional layer 13 is embedded in the primer layer 12, part or all of the gaps formed by the plurality of functional particles are filled with the components (especially adhesive resin) constituting the primer layer.

In the laminate of the second form, other layers may be included within the range not hindering the effect of the present invention, but it is preferable that the above-mentioned base material layer 11 and functional layer 13 are laminated so as to be directly in contact with each other.

In the embodiments shown in FIGS. 1 to 3 , part or all of the above-mentioned microparticle group 13a can also be firmly fixed by utilizing the strong adhesive force of the adhesive resin. That is, the microparticle groups 13a may be fixed in a state of being in direct contact with each other, or may be fixed to each other by an adhesive resin. In particular, the functional layer 13 is firmly fixed to the base material layer 11 by bonding the fine particles to each other through the adhesive resin (especially thermosetting resin).

The layered structure of the laminate of the present invention can be confirmed in cross-section using, for example, a scanning electron microscope, an optical microscope, or the like.

Hereinafter, each layer etc. which comprise the laminated body of this invention are demonstrated.

＜Substrate layer＞ The substrate layer is the layer that becomes the base (pedestal) of the laminate of the present invention, and has functions such as imparting rigidity and strength to the laminate.

The material constituting the base layer is not particularly limited. For example, resin films such as polyester film, polyethylene film, and polypropylene film, paper, synthetic paper, metal foil (aluminum foil, copper foil, etc.), metal plate, Simple materials such as non-woven fabrics, woven fabrics, wood, and glass plates, or their composite materials and laminates. Also, those in which a vapor-deposited layer containing metal components (aluminum, zinc, etc.) or inorganic components (silicon dioxide, alumina, etc.) is formed on the surface of these materials (for example, a resin film with a vapor-deposited layer) can also be used. Especially in the present invention, if an adhesive component is used in the primer layer, a laminate suitable for adhesion to all substrate layers and functional layers can be produced.

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

The thickness of the base material layer is not limited, and can be appropriately set according to the type of the packaged object when used as a packaging material or the like. Generally, it can be properly set within the range of about 9~500μm. Also, when a resin film is used for the base material layer, the following roughness treatment may be performed, for example, roughness treatment with a surface treatment agent or roughness treatment with embossing. In this case, the height of the concavo-convex can be set to about 5-60 μm, for example, or about 20-50 μm, but it is not limited thereto.

＜Primer coat＞ The primer layer mainly has the function of adhering and fixing the functional particles (or functional layer) to the substrate layer. In addition, it may also have a function of fixing the functional particles to each other in some cases.

The primer layer contains an adhesive resin, and part or all of the adhesive resin is made of a thermosetting resin. By using a thermosetting resin as the adhesive resin contained in the primer layer, the functional particles can be fixed more strongly, and as a result, high durability (sustained water repellency or oil repellency) can be exhibited. That is, by directly adhering the thermosetting resin to at least a part of the functional particles, the functional particles can be firmly fixed.

The content of the adhesive resin in the primer layer, for example, can be appropriately set within the range of 1-100% by mass (especially 90-100% by mass), but it is not limited thereto. The above content does not include the content of filler particles. Therefore, even when the filler particles are made of a heat-adhesive resin, for example, the content of the filler particles is not included in the content of the heat-adhesive resin.

thermosetting resin In the laminate of the present invention, part or all of the adhesive resin is a thermosetting resin. The proportion of the thermosetting resin in the adhesive resin is usually about 30 to 100% by mass, preferably within the range of 50 to 100% by mass. Therefore, for example, the whole (100% by mass) of the adhesive resin may be a thermosetting resin. Thereby, a high adhesive force can be exhibited compared with the case of using a thermoplastic resin, As a result, excellent abrasion resistance etc. can be acquired.

The thermosetting resin is not limited as long as it can be strongly bonded to the substrate layer and the functional particles (functional layer) after thermosetting, for example, phenol resin, urea resin, melamine resin, epoxy resin, unsaturated poly In addition to ester resins, polyurethane resins, diallyl phthalate resins, silicone resins, alkyd resins, etc., blended resins of these, and copolymers containing combinations of monomers constituting these can also be used , modified resin, etc. These can be used 1 type or 2 or more types. In particular, in the present invention, at least one of urea resin, melamine resin, epoxy resin, unsaturated polyester resin, polyurethane resin and alkyd resin can be suitably used. By using these thermosetting resins, higher adhesiveness can be obtained between the base material layer and the functional particles.

Among these thermosetting resins, at least one of polyurethane resin and melamine resin is particularly preferable because it can make the functional particles and the substrate layer adhere more strongly. When polyurethane resin or melamine resin is used as the thermosetting resin, even if the base layer is set to be any of plastic film, metal foil, paper, etc., it can be well adhered, and the functional particles and The adhesion of the substrate layer is further improved. That is, even if the functional particles or the functional layer are not easily peeled off due to friction, etc., it becomes a laminate that can exhibit water-repellent or oil-repellent properties with sustained force.

Also, the thermosetting resin may be either a one-component curing type or a two-component curing type. For example, by using a two-component curing thermoplastic resin, in addition to curing at a relatively low temperature, time until complete curing can be ensured, thereby contributing to the formation of a functional layer using functional particles, for example.

The content of the thermosetting resin in the primer layer is not limited, but it is generally set at 5% by mass or more, especially 10% by mass or more, and more preferably 20% by mass or more. Therefore, for example, you may set it as 50 mass % or more, or may set it as 60 mass % or more. The upper limit of the content can be usually set at 100% by mass, but it can also be set at 80% by mass, or 95% by mass, for example. Here, when the thermosetting resin is composed of the main ingredient and the curing agent, the total value of both is defined as the above-mentioned content. When the content of the thermosetting resin contained in the thermal adhesive resin is within the above range, durability can be obtained in at least one of water repellency and oil repellency. In addition, the content of the said thermosetting resin is content in the total 100 mass % including thermosetting resin, thermoplastic resin, filler particle|grains etc. in total.

filled particles It does not matter if filler particles are not included in the primer layer, but filler particles may also be included. The present invention covers either situation. Especially when filler particles are included, unevenness caused by filler particles will be formed on the surface of the functional layer side of the primer layer, and functional particles will be layered on the uneven surface, and multiple functional particles will also exist in the concave portion of the uneven surface. particle. Thereby, even when a part of the functional particles falls off due to strong friction or the like, the functional particles existing in the convex portion remain, whereby the water repellency and oil repellency can be more reliably maintained.

As the filler particles, in addition to particles composed of inorganic components or particles composed of organic components, particles containing both inorganic components and organic components may be used. Among them, it is more preferable to use at least one of acrylic resin particles, hydrophilic silica particles, calcium phosphate particles, carbon powder, calcined calcium particles, unfired calcium particles, calcium stearate particles, etc. good.

The shape of the filled particles is not limited, for example, it can be any one of spherical shape, spheroid shape, indeterminate shape, teardrop shape, flat shape, hollow shape, porous shape and the like.

There is no special limitation on the average particle size of the filling particles (by using a laser diffraction particle size distribution meter). Usually, it is preferably set at about 0.5-100 μm, especially 1-50 μm, and 5-30 μm optimal. Therefore, filler particles with an average particle diameter of about 20 to 90 μm can also be used. When the average particle diameter is less than 0.5 μm, it is not suitable in terms of handleability, formation of the aforementioned gaps, and the like. On the other hand, when the average particle diameter is larger than 100 μm, it is not suitable in terms of drop-off of filler particles, dispersibility, and the like.

Regarding the size of the filler particles, in the present invention, filler particles having a larger particle diameter than the functional particles are preferable. In particular, the minimum particle size of the filler particles should be greater than the maximum particle size of the composite particles. Since filler particles with a particle size larger than fine particles are included in the primer layer, unevenness is formed on the surface of the functional layer side of the primer layer, and many functional particles are accumulated on the uneven surface of the primer layer. There are a plurality of microparticle groups in the concave portion, so that even when a part of the functional particles falls due to strong friction, etc., the microparticle group existing in the concave portion remains to maintain super water repellency and super oil repellency.

The content when the filler particles are included in the primer layer can be appropriately changed according to the type of filler particles, desired physical properties, etc. Generally speaking, based on the weight of the solid content, the primer layer should be set at 1-90% by mass %, especially it is better to set it as 25-80 mass %, and it is best to set it as 30-70 mass %. Therefore, for example, it may be set to about 30 to 50% by mass, and further to 30 to 40% by mass. In addition, the said content is content in the total 100 mass % including thermosetting resin, thermoplastic resin, filler particle|grains etc. in total.

other ingredients In the primer layer, components other than the thermosetting resin may be contained within the range that does not inhibit the effect of the present invention. For example, a thermoplastic resin (heat-adhesive resin (heat-sealing material)), a tackifier, an antiblocking agent, a coloring material, a thickener, etc. are mentioned. In particular anti-caking agents may suitably be used. The type of anti-blocking agent is not particularly limited, for example, at least one of polyethylene wax, polypropylene wax, inorganic particles (silicon dioxide, etc.), synthetic resin particles, etc. may be added appropriately.

As the thermoplastic resin, known thermoplastic resins can be used. For example, in addition to acrylic resin, polystyrene, ABS resin, vinyl chloride resin, polyethylene resin, polypropylene resin, polyamide-based resin, polycarbonate, polyacetal, fluorine-based resin, etc., it is also possible to use these blended resins, copolymers containing combinations of monomers constituting them, modified resins, etc.

The content of the thermoplastic resin in the primer layer is not limited, and can be appropriately set within the range of 0-95% by mass (preferably 0-70% by mass). When imparting heat sealability to the primer layer, for example, Set it as 20-90 mass %. Specifically, by adding a thermoplastic resin to the primer layer, heat sealability can be imparted to the primer layer, and it can be used in applications (such as packaging materials) that are used after heat sealing. On the other hand, in applications where it is not necessary to impart heat-sealability, etc., the primer layer can be changed even under severe conditions when either no thermoplastic resin is contained or it is within the range of 10% by mass or less. It is ideal to use it reliably. The content of the above thermoplastic resin does not include the content of filler particles. Therefore, even when the filler particles are made of a thermoplastic resin, for example, the content of the filler particles is not included in the content of the thermoplastic resin.

The thickness of the primer layer is not particularly limited. In addition to adhesiveness, it is generally suitable to be about 0.01 μm~5 mm, especially about 0.01 μm~2 mm from the viewpoints of productivity and cost.

Also, there is no special limitation on the formation amount of the primer layer, but it is usually preferably 0.5~100g/m ² based on the solid content of the adhesive resin, especially preferably 1~100g/m ² , and 2~100g/m 2 in particular. 7g/ ^m2 is the best. If the formation amount of the adhesive resin is less than 0.5 g/m ² , the adhesiveness of the functional particles may be insufficient and the durability may be lowered. On the other hand, if the aforementioned forming amount exceeds 100 g/m ² , the primer layer may be damaged when strong stress is applied to the laminate.

The ratio [A/(A+B)] of the adhesive resin to the total amount of the adhesive resin (A) and the functional particles (B) is not particularly limited, and generally can be appropriately within the range of about 5~97% by mass set up. The above-mentioned ratio [A/(A+B)] is especially preferably set at 5-91 mass %, more preferably set at 10-87 mass %, and particularly preferably set at 14-50 mass %. When the said ratio is less than 5 mass %, the adhesiveness of an adhesive resin and a base material will become insufficient, and there exists a possibility that durability may fall. Also, when the ratio exceeds 91% by mass, the functional particles may not be able to sufficiently form a desired three-dimensional network structure, which may impair the water-repellent and oil-repellent properties.

Formation method of primer layer The method for forming the primer layer is not particularly limited, and it can be implemented by, for example, applying a coating liquid for forming a primer layer on the substrate layer and drying it. Moreover, as will be described later, when the functional particles are provided, the primer layer may be formed simultaneously with the provision of the functional particles.

As the coating liquid for forming the primer layer, at least an adhesive resin dissolved in a solvent or a dispersion dispersed in a solvent can be used. In addition, as the adhesive resin, other than the above-described thermosetting resin itself, its raw materials (main agent and curing agent) can also be used. In addition, the aforementioned filler particles, thermoplastic resin, and the like may be blended into the coating liquid as needed.

The solvent is not limited, for example, in addition to water, ethanol, methanol, cyclohexane, toluene, acetone, isopropanol (IPA), propylene glycol, hexanediol, butyl diglycol, 1,5- Pentylene glycol, n-pentane, n-hexane, hexanol, methyl ethyl ketone, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, isoamyl acetate, n-butyl acetate Esters, n-propyl acetate, n-pentyl acetate (alias: n-amyl acetate), cyclohexane, isobutanol, isopropanol, isoamyl alcohol, diethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether, ethylene glycol monomethyl ether, o-dichlorobenzene, xylene, cresol, chlorobenzene, cyclohexanol, cyclohexane Ketones, N,N-dimethylformamide, tetrahydrofuran, 1,1,1-trichloroethane, toluene, etc. These can be used 1 type or 2 or more types.

The solid content concentration and the like of the coating liquid for forming a primer layer can be appropriately set in consideration of applicability and the like, for example, in a range of about 5 to 60% by mass, but is not limited thereto.

The preparation method of the coating liquid for primer layer formation is not specifically limited, It can prepare by adding adhesive resin etc. to a solvent, and mixing. In addition, the order of adding each component is not particularly limited.

The method of coating with the coating liquid for forming the primer layer is not particularly limited, and for example, roll coating, various gravure coatings, rod coaters, doctor blade coating, chipped wheel coaters, spray coatings, etc. can be used. It is coated on the substrate layer by known methods such as coating and brush coating. Also, when filler particles are included in the coating liquid for forming the primer layer, the filler particles and the like may be added to a solvent together with the adhesive resin (main agent and hardener), mixed, and coated by the above-mentioned coating method. distributed on the base layer.

Next, the formed coating film is dried. By drying, the solvent can be evaporated and a primer layer can be formed on the substrate layer. Drying conditions can be suitably set according to the kind of solvent, coating amount, etc., for example. The temperature can be set within the range of 50-250°C, for example, but not limited thereto. Also, the drying time can be within the range of 5 seconds to 60 minutes, but it is not limited thereto.

By this drying, part or all of the thermosetting resin contained in the coating film is cured. As will be described later, when the functional layer is laminated on the primer layer, if the thermosetting resin contained in the primer layer is in a semi-cured state when the functional layer is laminated, the functional particles will sink to a part of the surface of the primer layer, and the functional particles will sink to a part of the surface of the primer layer. Since it becomes difficult to fall off, it is preferable. As a method of semi-hardening the thermosetting resin contained in the primer layer, for example, a) a method of adjusting the above-mentioned drying temperature or time, b) a method of adjusting the curing temperature or time of the primer layer formed after drying can be used. Thereby, the hardening state of the thermosetting resin can be controlled. For example, the drying condition may be set at a drying temperature of about 90-120° C., but is not limited thereto. Also, the drying time can be set to about 30-90 seconds (especially 30-60 seconds), but it is not limited thereto. Also, when the thermosetting resin is also in a semi-cured state after the functional layer has been laminated, the thermosetting resin may be completely cured in the drying step when the functional layer is formed.

＜Functional layer＞ In the present invention, the functional layer is a layer in which functional particles are fixed to each other in a three-dimensional network structure. By having such a composition and structure, adhesion of water, oil, etc. can be prevented, and thus it has a function as an antiadhesion layer of the laminate of the present invention.

Functional Particles Hydrophobic particles or oleophobic particles can be used according to desired functions and the like.

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 preferred.

In addition, hydrophobic oxide particles, etc. can also be used as hydrophobic particles. For example, hydrophilic fine particles that have been hydrophilized by etching, ultraviolet irradiation, sandblasting, plasma treatment, etc. are hydrophobized with a silane coupling agent to make the local Hydroxyl group remains. By forming these functional layers with a three-dimensional mesh structure, the surface on the primer layer side can be strongly bonded to the thermosetting resin, and the other side can also exhibit super water repellency and/or super oil repellency.

The average primary particle size of the inorganic oxide particles is preferably 5-50 nm, especially 7-30 nm. In addition, the measurement of the average primary particle diameter of an inorganic oxide particle can be implemented using a transmission electron microscope or a scanning electron microscope. More specifically, the average primary particle size can be obtained by taking a picture with a transmission electron microscope or a scanning electron microscope, measuring the diameters of more than 200 particles on the picture, and calculating the arithmetic mean.

The aforementioned nanoscale inorganic oxide particles are not limited, and known or commercially available ones can also be used. For example, silicon dioxide can include: product names "AEROSIL R972", "AEROSIL R972V", "AEROSIL R972CF", "AEROSIL R974", "AEROSIL RX200", "AEROSIL RY200" (the above are shares of Japan AEROSIL) Co., Ltd.), "AEROSIL R202", "AEROSIL R805", "AEROSIL R812", "AEROSIL R812S" (the above are manufactured by EVONIK DEGUSSA), "SYLOPHOBIC100", "SYLOPHOBIC200", "SYLOPHOBIC603 "(The above is manufactured by Fuji Silicon (FUJI SILYSIA) Chemical Co., Ltd.), etc. Examples of titanium dioxide include product name "AEROXIDE TiO ₂ T805" (manufactured by EVONIK DEGUSSA). Alumina can be exemplified by fine particles treated with a silane coupling agent such as "AEROXIDE Alu C" (manufactured by EVONIK DEGUSSA) with the product name "AEROXIDE Alu C" to make the particle surface hydrophobic.

Among them, hydrophobic silica fine particles can be suitably used. In particular, hydrophobic silica microparticles having trimethylsilyl groups on the surface are preferable in terms of obtaining more excellent non-adhesive properties. Commercially available products corresponding thereto include, for example, the above-mentioned "AEROSIL R812" and "AEROSIL R812S" (both manufactured by Evonik Degussa) and the like.

The adhesion amount (weight after drying) of hydrophobic particles is not limited, and it can usually be set within the range of 0.01~100g/m ² , especially 0.01~10g/m ² is better, and then 0.2 ~1.5g/ ^m2 is better, and 0.2~1g/ ^m2 is the best.

As the oleophobic particles, composite particles including: a) inorganic oxide particles; and b) a coating layer formed on the surface thereof and containing polyfluoroalkyl methacrylate resin can be used. By having a layer body containing composite particles, adhesion to oil itself or components rich in oil can also be reduced. The particle size of the oil-repelling composite particles can be suitably used within the same range as that of the above-mentioned water-repelling inorganic oxide particles.

As composite particles with oil repellency, silicon oxide can be used under the product name "AEROSIL 200"("AEROSIL" is a registered trademark, the same below), "AEROSIL 130", "AEROSIL 300", "AEROSIL 50", "AEROSIL 200FAD ", "AEROSIL 380" (above are manufactured by Nippon Aerosil (AEROSIL) Co., Ltd.), and the like. The particles exemplified are oil-repellent particles whose core surface is coated with a polyfluoroalkyl methacrylate resin. As the titanium oxide, particles exemplified by the product name "AEROXIDE TiO ₂ T805" (manufactured by EVONIK DEGUSSA) and the like are used as the core, and the surface of the core is coated with a polyfluoroalkyl methacrylate resin. Oleophobic particles. As alumina, particles exemplified by the product name "AEROXIDE Alu C 805" (manufactured by EVONIK DEGUSSA) are used as cores, and the surface of the cores is coated with a polyfluoroalkyl methacrylate resin. things.

The polyfluoroalkyl methacrylate resin used as the coating layer has excellent affinity with the oxide particles (especially silicon oxide particles) that become the core as described above, so it can form a high adhesion on the surface of the particles. The strong coating layer can also show high water repellency and oil repellency at the same time. As such a resin itself, known or commercially available ones can be used. Commercially available products include, for example: product name "CHEMINOX FAMAC-6" (manufactured by UNIMATEC (Japan) Co., Ltd.), product name "Zonyl TH Fluoromonomer code 421480" (Sigma Aldrich (SIGMA-ALDRICH) (USA) ) company), product name "SCFC-65530-66-7" (Maya High Purity Chemicals (Maya High Purity Chem) (China) company), product name "FC07-04~10" (Fluory, Inc (USA) )), product name "CBINDEX: 58" (manufactured by Wilshire Chemical Co., Inc (USA)), product names "AsahiGuard AG-E530", "AsahiGuard AG-E060" (both Asahi Glass Co., Ltd.), product name "TEMAc-N" (Top Fluorochem Co., LTD (China) company), product name "Zonyl 7950" (SIGMA-RBI (Switzerland) company), product name "6100840~6100842 "(Weibo Chemcal Co., Ltd) (China) company), product name "CB INDEX: 75" (ABCR GmbH & CO.KG (Germany) company), etc.

Among them, from the standpoint of obtaining more excellent oil repellency or even water repellency, for example, a) polyfluorooctyl methacrylate, b) 2-N,N-diethylamine ethyl A copolymer of methacrylate, c) 2-hydroxyethyl methacrylate and d) 2,2'-ethylenedioxydiethyl dimethacrylate is used as the above-mentioned resin. These can also use the above-mentioned commercially available items. This commercially available product is in the form of an aqueous dispersion, but may be in other forms.

The method of coating the core surface with polyfluoroalkyl methacrylate resin (preparation method of composite particles) is not particularly limited, as long as the core particle (powder) is coated with polyfluoroalkyl methacrylate resin and followed A known coating method, granulation method, etc. may be used to form the coating layer. For example, composite oxide fine particles can be appropriately prepared by a production method including a step (coating step) of applying a liquid agent (liquid agent) to inorganic oxide particles, and the liquid agent is a liquid polyfluoroalkylmethyl Acrylic resin is dissolved or dispersed in a solvent.

In the above production method, the polyfluoroalkyl methacrylate resin can be suitably used as a liquid at normal temperature (25° C.) and normal pressure. As such a polyfluoroalkyl methacrylate resin, the commercially available ones exemplified above can also be used.

The solvent used in the liquid preparation is not particularly limited. Besides water, organic solvents such as alcohol and toluene can also be used, but water is preferably used in the present invention. That is, it is preferable to use a) an aqueous solution in which the polyfluoroalkyl methacrylate resin has been dissolved in water; and/or b) a dispersion in which the polyfluoroalkyl methacrylate resin has been dispersed in water.

The content of the polyfluoroalkyl methacrylate resin in the above-mentioned solution is not particularly limited, and it is generally set at 10-80% by mass, especially preferably within the range of 20-60% by mass.

The method of coating the liquid agent on the surface of the core particles may follow a known method, for example, any of spraying method, dipping method and the like can be applied. Especially in the present invention, in terms of excellent uniformity and the like, coating by a spray method is particularly preferable.

After coating the liquid agent, the coated particles can be produced by removing the solvent by heat treatment. The heat treatment temperature should generally be set at about 150-250°C, especially 180-200°C. The gas environment for heat treatment is not limited, but it is preferably an inert gas environment such as nitrogen or argon. Also, for example, a series of steps consisting of a coating step and a heat treatment step may be further performed one or more times as needed. Thereby, control of the amount of coating etc. can be performed suitably.

The amount of oil-repelling particles attached (weight after drying) is not limited, and can usually be set within the range of 0.01~100g/m ² . In particular, it is better to set it at 0.5~100g/m ² , and more preferably to set it at 1~100g/m ² , and it is more preferable to set it at 15~100g/m ² .

＜Method of Imparting Functional Particles＞ The method of imparting functional particles such as the primer layer is not limited, and examples include: (a) a method comprising the step of applying a dispersion liquid in which the functional particles have been dispersed in a solvent to the surface of the primer layer; (b) comprising The method of the step of applying the mixed solution containing functional particles and primer components to the surface of the substrate layer, etc. These may also be used in combination. More specifically, it can be appropriately selected according to the structure and structure of the laminate of the present invention. Representative examples are shown below.

The case of the laminated body of the first form For example, as shown in FIG. 1 , the first form is a structure in which functional particles are substantially fixed to the primer layer.

The method of imparting the functional particles is not particularly limited, and in particular, it can be suitably implemented by a method including the step of applying a dispersion liquid in which the functional particles are dispersed in a solvent to the surface of the primer layer.

The solvent used in the above-mentioned dispersion liquid is not particularly limited, for example, besides water, also can enumerate: alcohol (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexanediol, butyl diglycol, 1 , 5-pentanediol, n-pentane, n-hexane, hexanol, etc.

The content of functional particles in the dispersion can be determined appropriately within the range of 20-50 g/L (liter), depending on the type of functional particles, the degree of water repellency and oil repellency, etc., for example.

The method of applying the dispersion to the surface of the material is not limited, and known methods can be used. For example, known methods such as roll coating, gravure coating, bar coating, doctor blade coating, chipping wheel coating, and brush coating can all be used. The amount of coating when the dispersion is applied is preferably adjusted so that the weight of the composite particles becomes the above-mentioned adhesion amount after the coating film dries.

After the dispersion is applied to the surface of the material, a drying step is carried out. Drying may be either natural drying or heat drying. The temperature at the time of heat drying is not specifically limited, Usually, it should just be 100 degreeC or less (preferably 90-100 degreeC). Also, the drying time can be set to about 30-90 seconds (especially 30-60 seconds), but it is not limited thereto.

Layered body of the second form For example, as shown in FIG. 2 , the second form is a structure in which functional particles are fixed in and on the primer layer.

In this case, the functional particles can be appropriately imparted by a method including the step of applying a mixture containing an adhesive resin and functional particles to the surface of the substrate layer or the surface of the primer layer. When this mixed solution is applied to the surface of the substrate layer, the provision of functional particles and the formation of the primer layer can be performed simultaneously. As the above-mentioned primer layer, the mixed liquid may be applied to the layer body formed in advance with the coating liquid for forming a primer layer as described above.

The solvent used in the above-mentioned mixed solution is not particularly limited. For example, in addition to water, ethanol, methanol, cyclohexane, toluene, acetone, isopropyl alcohol (IPA), propylene glycol, hexanediol, butyl diol, etc. Glycol, 1,5-pentanediol, n-pentane, n-hexane, hexanol, methyl ethyl ketone, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, acetic acid Isoamyl ester, n-butyl acetate, n-propyl acetate, n-pentyl acetate (alias n-amyl acetate), cyclohexane, isobutanol, isopropanol, Isoamyl alcohol, diethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether, ethylene glycol monomethyl ether, o-dichlorobenzene, xylene, cresol, chlorobenzene, Cyclohexanol, cyclohexanone, N,N-dimethylformamide, tetrahydrofuran, 1,1,1-trichloroethane, toluene, etc. These can be used 1 type or 2 or more types. Moreover, it can select suitably according to the kind of adhesive resin etc. to be used.

The contents of the adhesive resin and functional particles in the mixed solution can be adjusted to the aforementioned ratio [A/(A+B)], which can be appropriately determined according to the type of functional particles, the degree of water repellency and oil repellency, etc.

Moreover, although the solid content of a mixed liquid can be made into the range of about 1-60 mass %, for example, it is not limited to this. Therefore, for example, you may set it as 5-25 mass % (especially 5-20 mass %). Thereby, for example, functional particles can be exposed more reliably.

The method of applying the mixed liquid to the surface of the material is not limited, and known methods can be used. For example, known methods such as roll coating, gravure coating, bar coating, doctor blade coating, chipping wheel coating, and brush coating can all be used. When coating the dispersion liquid, the coating amount is preferably adjusted so that the weight of the functional particles after the coating film dries becomes the above-mentioned adhesion amount.

In the present invention, after the mixed solution is applied, generally speaking, the components (adhesive resin, etc.) forming the primer layer will move toward the substrate layer side (below) by gravity, and a part of the functional particles can appear The state exposed on the surface. Therefore, for example, a liquid mixture that has sufficient drying or hardening time after coating to expose the functional particles can also be suitably used. In the present invention, especially by setting the ratio of the adhesive resin to the functional particles within the range of the aforementioned ratio [A/(A+B)], the functional particles (especially the functional layer) can be made more reliably Appears in the state of being exposed on the surface of the laminate.

After coating the mixed solution on the surface of the material, the drying step can be carried out. Drying may be either natural drying or heat drying. When heating and drying, what is necessary is just to heat at about 150 degreeC or less (preferably 90-145 degreeC) normally. The drying time can be set to about 30-90 seconds, for example, but it is not limited thereto.

Accordingly, by using the second embodiment of the manufacturing method, it is possible to form a structure in which a part of the functional particles is buried in the primer layer, and the rest are exposed. That is, a part of the functional particles can enter the primer layer, and the other part of the functional particles is a) exposed from the primer layer; or b) deposited on the primer layer. By embedding a part of the functional layer in a part of the primer layer, the functional particles adhere to the primer layer more strongly to improve durability, and by exposing a part of the functional particle layer from the primer layer, And can get more excellent water repellency and oil repellency. As a result, excellent water repellency and oil repellency can be maintained even under severe use conditions or long-term use conditions.

The method of embedding part of the functional particles constituting such a functional layer in the primer layer can be used in addition to the method of using the above-mentioned mixed solution, 1) a dispersion coating comprising the functional particles dispersed in a solvent. 2) a method including the step of coating the surface of the primer layer with a dispersion liquid in which the functional particles have been dispersed in a solvent before the thermal curing is completed.

The method of the aforementioned 1) may employ a method such as bringing the pressurizing plate into contact with the functional particles (particle group) accumulated on the primer layer, and pressing the pressurizing plate etc. downward in the thickness direction.

In the method of 2) above, the dispersion liquid is applied to the primer layer before the thermal curing is completed. Therefore, the thermosetting resin contained in the adhesive resin in the primer layer will harden, and the process until the curing is completed Among them, the functional particles are partly embedded in the primer layer due to their own weight or the hardening reaction of being absorbed into the primer layer. In this case, a method of pressing functional particles may also be used in combination if necessary. Here, "before thermal curing is completed" includes, for example, any of the wet state immediately after coating of the primer layer forming coating liquid, the naturally dried state, and the semi-cured state in which the drying progresses but is not fully cured. a state.

Example Examples and comparative examples are shown below, and the characteristics of the present invention will be described more specifically. However, the scope of the present invention is not limited to the Examples.

Example 1 (1) Making a substrate sheet as an adhesive resin, compared to a two-component hardening type urethane resin (which has been mixed with Di Aixi ink (DIC) at a weight ratio of 10:1, which is a thermosetting resin The main ingredient polyester polyurethane polyol (LX500) manufactured by Graphics) and toluene diisocyanate (KW75) of the same company as a hardening agent were made into a solid content of 32% by mass and dissolved in ethyl acetate which is a solvent Thin) 21 parts by weight, adding acrylic modified polyolefin resin (APO, 300214-1 manufactured by Tanaka Chemical Co., Ltd., which has a solid content of 20% by mass and dissolved in ethanol which is a solvent) which is a thermoplastic resin) 304 parts by weight, and the ratio of the urethane resin to the acrylic modified polyolefin resin is prepared in such a way that the ratio of the solid content becomes 10% by mass to 90% by mass (coating liquid for forming the primer layer, Same below). At this time, the total solid content was adjusted to 10% by mass using ethyl acetate. 5 parts by weight of polyethylene beads (product name "MIPELON (registered trademark) XM-221U" manufactured by Mitsui Chemicals Co., Ltd., average particle size: 25 μm, melting point: 136° C.) were added to 100 parts by weight of the primer solution as The particles were filled and stirred at room temperature for 30 minutes to prepare a coating liquid. Using a bar coater #6, apply this coating solution to a thickness of 30 μm constituting the substrate layer so that the weight after drying becomes 7.5 g/m ² and the dry weight of the adhesive resin becomes 5.0 g/m ² Aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) was placed on the surface, and then heated and dried in an oven at 100° C. for 40 seconds to evaporate the solvent, thereby producing a substrate sheet on which a primer layer was laminated on the aluminum foil. (2) Preparation of Composite Particles (2-1) Preparation of Fluorine-Containing Composite Particles Hydrophilic silica particles (product name "AEROSIL 200", manufactured by Japan AEROSIL Co., Ltd., with a BET specific surface area of 200 m ² /g , average primary particle size 12nm) 100g was put into the reaction tank, and 500g of a commercially available surface treatment agent was sprayed while stirring under a nitrogen atmosphere, and then cooled at 200° C. for 30 minutes after stirring. In this way, a powder composed of composite particles can be produced. In addition, the above-mentioned surface treatment agent uses polyfluorooctyl methacrylate, 2-N,N-diethylamine ethyl methacrylate, 2-hydroxyethyl methacrylate and 2,2'-ethylene Aqueous dispersion of copolymer of dioxydiethyl dimethacrylate (solid content concentration: 20% by mass). (2-2) Preparation of Dispersion Liquid Containing Composite Particles A dispersion liquid was prepared by adding and mixing 44 parts by weight of the prepared composite particles in 56 parts by weight of ethanol. (3) Fabrication of a laminate Add ethanol to the dispersion liquid obtained in the above (2) to prepare a composite particle coating liquid with a solid content of 10% by mass, and use a rod coater #3 to coat the above-mentioned (1) ) on the surface of the substrate sheet on which the primer layer was laminated, and heated and dried in an oven at 100°C for 40 seconds to evaporate ethanol, thereby obtaining a thermosetting resin containing 10% by mass of the substrate layer in sequence A laminate sample of the primer layer and the functional layer of the adhesive resin. In addition, the target layered amount of the composite particles was set to 3.0 g/m ² as the weight after drying.

Example 2 A laminate sample was prepared in the same manner as in Example 1, except that the primer solution was prepared such that the urethane resin and the acrylic modified polyolefin resin became 30% by mass to 70% by mass.

Example 3 The primer solution was prepared in the same manner as in Example 1, except that the solid content ratio of the urethane resin and the acrylic modified polyolefin resin (APO) was 50% by mass to 50% by mass. laminate samples.

Example 4 Dissolve the urethane resin in the primer solution and the maleic anhydride modified polyolefin resin (MAPO) (TANAKA Chemical Co., Ltd.) 290628-2, which is a thermoplastic resin instead of the acrylic modified polyolefin resin. The primer liquid is prepared in such a way that the solid content ratio becomes 50 mass % to 50 mass % in AP-NT solvent of the same company as a solvent, and the solid content is 20 mass %, and it will be used for the substrate sheet The base material was changed from aluminum foil to linear low-density polyethylene (LLDPE, LIX (registered trademark) film L4102 manufactured by Toyobo Co., Ltd., with corona treatment on the surface) with a thickness of 50 μm. In addition, the setting and implementation In the same manner as in Example 1, a laminate sample was prepared.

Example 5 A laminate sample was produced in the same manner as in Example 1 except that the urethane resin in the primer solution was 100% by mass.

Example 6 Except that the amount of the primer solution applied to the base sheet was set to a dry weight of 0.75 g/m ² , and the dry weight of the adhesive resin was set to 0.5 g/m ² , it was the same as in Example 5. A laminate sample was prepared.

Example 7 Except that the amount of the primer solution applied to the base sheet was set to 1.5 g/m ² after drying, and the dry weight of the adhesive resin was 1.0 g/m ² , it was the same as in Example 5. A laminate sample was prepared.

Example 8 It was prepared in the same manner as in Example 5, except that the amount of the primer solution applied to the base sheet was set at 15 g/m ² after drying, and the dry weight of the adhesive resin was 10.0 g/m ² . Obtain laminate samples.

Example 9 It was prepared in the same manner as in Example 5, except that the amount of the primer solution applied to the base sheet was 150 g/m ² after drying, and the dry weight of the adhesive resin was 100.0 g/m ² . Obtain laminate samples.

Example 10 A laminate sample was prepared in the same manner as in Example 5, except that the target laminated amount of composite particles for the dry weight functional layer was changed from 3.0 g/m ² to 0.3 g/m ² .

Example 11 A laminate sample was prepared in the same manner as in Example 5, except that the target laminated amount of composite particles for the dry weight functional layer was changed from 3.0 g/m ² to 0.5 g/m ² .

Example 12 A laminate sample was prepared in the same manner as in Example 5, except that the target laminated amount of composite particles for the dry weight functional layer was changed from 3.0 g/m ² to 1.0 g/m ² .

Example 13 A laminate sample was prepared in the same manner as in Example 5, except that the target laminated amount of composite particles for the dry weight functional layer was changed from 3.0 g/m ² to 15.0 g/m ² .

Example 14 A laminate sample was prepared in the same manner as in Example 5, except that the target laminated amount of composite particles for the dry weight functional layer was changed from 3.0 g/m ² to 100.0 g/m ² . In addition, since the target layering amount of composite particles of 100.0g/ ^m2 cannot be laminated with a bar coater at one time, it is repeatedly applied with a bar coater and dried, then the dry weight is measured, and the bar coater is applied again. This step is to measure the dry weight after machine coating and drying.

Example 15 Change the thermosetting resin from urethane resin to isocyanate (KW75 toluene diisocyanate manufactured by DIC Graphics was dissolved in ethyl acetate which is a solvent with a solid content of 20% by mass) , after making a sample to obtain a sample with a substrate layer, a primer layer and a functional layer in sequence, the prepared sample was cured at 40°C×75RH% for 2 days to convert the isocyanate into a urea resin, Except for this, a laminate sample was produced in the same manner as in Example 5.

Example 16 Except that the base material used for the base sheet was changed from aluminum foil to biaxially stretched polypropylene (OPP, Toyobo Co., Ltd. P2102, corona-treated surface) with a thickness of 20 μm, a laminate was obtained in the same manner as in Example 5. Sample.

Example 17 A laminate sample was produced in the same manner as in Example 5, except that the urethane resin was 100% by mass, no thermoplastic resin was added, and filler particles were not further added to the primer solution.

Example 18 In addition to setting the adhesive resin as a mixture of 50 parts by weight of epoxy resin (100% epoxy resin, the main ingredient of adhesive No. 31 manufactured by Daiso Co., Ltd.) and melamine resin (DIA DIC Graphics (manufactured by DIC Graphics, TF842 Heat Resistant Reinforcing Agent) 50 parts by weight to make a solid content of 20% by mass and dissolve in ethyl acetate which is a solvent, no thermoplastic resin added, thermosetting resin in the primer layer The ratio was set at 100% by mass, and a laminate sample was obtained in the same manner as in Example 1, except that filler particles were not further added to the primer liquid.

Example 19 In addition to setting the adhesive resin as an epoxy resin that is a thermosetting resin (100% of the main agent epoxy resin of Adhesive No. 31 manufactured by DAISO Co., Ltd. and polysulfide as a hardener in a ratio of 1:1) Alcohol 100%) as a solid content of 20% by mass and dissolved in ethyl acetate which is a solvent, no thermoplastic resin is added, the ratio of thermosetting resin in the primer layer is set to 100% by mass, no further A laminate sample was obtained in the same manner as in Example 1 except that filler particles were added to this primer liquid.

Example 20 In addition to adding 10 parts by weight of polyethylene beads (product name "MIPELON (registered trademark) XM-221U" manufactured by Mitsui Chemicals Co., Ltd., average particle size: 25 μm, melting point: 136°C) to 100 parts by weight of the primer solution as The particles were filled and stirred at room temperature for 30 minutes, and a laminate sample was obtained in the same manner as in Example 19.

Example 21 Except that the adhesive resin is 100 parts by weight of unsaturated polyester resin (5013PT light-colored transparent FRP resin non-paraffin wax manufactured by PROST) which is a thermosetting resin and dissolved at a solid content of 20% by mass. Except that ethyl acetate is a solvent, no thermoplastic resin is added, the ratio of the thermosetting resin in the primer layer is set to 100% by mass, and filler particles are not further added to the primer liquid, it is set to the same as the embodiment. In the same manner as in 1, a laminate sample was prepared.

Example 22 Except that the adhesive resin was set to 100 parts by weight of alkyd resin (WOOD LOVE company oil finish (oil finish)), no thermoplastic resin was added, and the proportion of thermosetting resin in the primer layer was set to 100% by mass, no further steps were made. A laminate sample was obtained in the same manner as in Example 1 except that filler particles were added to the primer liquid.

Example 23 Except that the adhesive resin is 100 parts by weight of silicone resin (Daiso (DAISO) Co., Ltd. repair agent A No. 1 silicone repair agent) and the solid content is 20% by mass, and it is dissolved in distilled water which is a solvent. without adding a thermoplastic resin, setting the ratio of the thermosetting resin in the primer layer to 100% by mass, and not adding filler particles to the primer solution, the laminate was obtained in the same manner as in Example 1. Sample.

Example 24 As an adhesive resin, a two-component hardening type urethane resin (a main agent made by DIC Graphics, which has been blended at a weight ratio of 10:1) is a thermosetting resin. Polyurethane polyol (LX500) and the company's toluene diisocyanate (KW75) as a hardener were dissolved in ethyl acetate as a solvent with a solid content of 32% by mass) 44.6 parts by weight, adding Ethyl acetate has been added to the composite particles prepared in "(2) Preparation of composite particles" in Example 1 to make 857 parts by weight of a coating solution containing composite particles at 10% by mass, and urethane resin A mixed solution was prepared so that the ratio to the composite particles would be 14% by mass to 86% by mass in terms of solid content. At this time, the total solid content was set to 10% by mass using ethyl acetate, and stirred at room temperature for 30 minutes to prepare a coating liquid. Using a bar coater #12, apply the coating solution to the base material layer so that the weight after drying is 3.5 g/m ² and the dry weight of the adhesive resin is 0.5 g/m ² On the surface of an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) with a thickness of 30 μm, and then heated and dried in an oven at 140° C. for 40 seconds to evaporate the solvent, thereby obtaining a primer layer containing composite particles on the aluminum foil and functional layer laminate samples.

Example 25 As an adhesive resin, a two-component hardening type urethane resin that is a thermosetting resin (a main agent made by DIC Graphics has been blended at a weight ratio of 10:1) Polyester polyurethane polyol (LX500) and toluene diisocyanate (KW75) of the same company as a hardening agent are dissolved in ethyl acetate which is a solvent with a solid content of 32% by mass) 272 parts by weight, add Ethyl acetate has been added to the composite particles prepared in "(2) Preparation of composite particles" in Example 1 to make 130 parts by weight of a coating solution containing composite particles at 10% by mass, and urethane resin A mixed solution was prepared so that the ratio to the composite particles would be 87% by mass to 13% by mass in terms of solid content. At this time, the total solid content was set to 10% by mass using ethyl acetate, and stirred at room temperature for 30 minutes to prepare a coating liquid. Using a rod coater #28, apply the coating solution to the thickness of the substrate layer so that the weight after drying is 11.5g/m ² and the dry weight of the adhesive resin is 10g/m ² The surface of a 30 μm aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) was then heated and dried in an oven at 140° C. for 60 seconds to evaporate the solvent. Then, the same operation was carried out again using the above-mentioned coating solution, whereby a laminate sample having a primer layer containing composite particles and a functional layer on the aluminum foil was produced. The total dry weight of the primer layer and the composite particles is 23g/m ² , and the dry weight of the adhesive resin is 20g/m ² .

Example 26 As an adhesive resin, a two-component hardening type urethane resin (a main agent made by DIC Graphics, which has been blended at a weight ratio of 10:1) is a thermosetting resin. Polyurethane polyol (LX500) and the company's toluene diisocyanate (KW75) as a hardening agent were dissolved in ethyl acetate as a solvent with a solid content of 32% by mass) 284 parts by weight, adding Ethyl acetate has been added to the composite particles prepared in "(2) Preparation of composite particles" in Example 1 to make 10% by mass of 91 parts by weight of a coating solution containing composite particles, and urethane resin A mixed solution was prepared so that the ratio to the composite particles would be 91% by mass to 9% by mass in terms of solid content. At this time, the total solid content was set to 15% by mass using ethyl acetate, and stirred at room temperature for 30 minutes to prepare a coating liquid. Using a bar coater #14, apply the coating solution to the thickness of the substrate layer so that the weight after drying is 5.5 g/m ² and the dry weight of the adhesive resin is 5 g/m ² On the surface of 30 μm aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30), and then heated and dried in an oven at 140° C. for 40 seconds to evaporate the solvent, thereby obtaining a primer layer containing composite particles and a functional layer. laminate samples.

Example 27 As an adhesive resin, a two-component hardening type urethane resin (a main agent made by DIC Graphics) was blended at a weight ratio of 10:1, which is a thermosetting resin. Polyurethane polyol (LX500) and the company's toluene diisocyanate (KW75) as a hardening agent were dissolved in ethyl acetate as a solvent with a solid content of 32% by mass) 78.1 parts by weight, adding Ethyl acetate has been added to the composite particles prepared in "(2) Preparation of composite particles" in Example 1 to make 10% by mass of 750 parts by weight of a coating solution containing composite particles, and urethane resin A mixed solution was prepared so that the ratio to the composite particles was 25% by mass to 75% by mass in terms of solid content ratio. At this time, the total solid content was set to 10% by mass using ethyl acetate, and stirred at room temperature for 30 minutes to prepare a coating liquid. Using a bar coater #22, apply the coating solution to the thickness of the base material layer so that the weight after drying is 10g/m ² and the dry weight of the adhesive resin is 2.5g/m ² The surface of a 30 μm aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) was then heated and dried in an oven at 140° C. for 60 seconds to evaporate the solvent. Then, the same operation was carried out again using the above-mentioned coating solution, whereby a laminate sample having a primer layer containing composite particles and a functional layer on the aluminum foil was produced. The total dry weight of the primer layer and the composite particles is 20g/m ² , and the dry weight of the adhesive resin is 5g/m ² .

Example 28 As an adhesive resin, a two-component hardening type urethane resin (a main agent made by DIC Graphics) was blended at a weight ratio of 10:1, which is a thermosetting resin. Polyurethane polyol (LX500) and the company's toluene diisocyanate (KW75) as a hardening agent were dissolved in ethyl acetate as a solvent with a solid content of 32% by mass) 14.9 parts by weight, adding Ethyl acetate has been added to the composite particles prepared in "(2) Preparation of composite particles" in Example 1 to make 952 parts by weight of a coating solution containing composite particles at 10% by mass, and urethane resin A mixed solution was prepared so that the ratio to the composite particle was 5% by mass to 95% by mass in terms of solid content ratio. At this time, the total solid content was set to 10% by mass using ethyl acetate, and stirred at room temperature for 30 minutes to prepare a coating liquid. Using a bar coater #22, apply the coating solution to the thickness of the base material layer so that the weight after drying is 10g/m ² and the dry weight of the adhesive resin is 0.5g/m ² The surface of a 30 μm aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) was then heated and dried in an oven at 140° C. for 60 seconds to evaporate the solvent. Then, the same operation was repeated using the aforementioned coating liquid, whereby a laminate sample having a primer layer containing composite particles and a functional layer on the aluminum foil was produced. The total dry weight of the primer layer and the composite particles is 105g/m ² , and the dry weight of the adhesive resin is 5g/m ² .

Example 29 As an adhesive resin, a two-component hardening type urethane resin (a main component polymer made by DIC Graphics was blended at a weight ratio of 10:1), which is a thermosetting resin, was used. Polyurethane polyol (LX500) and the company's toluene diisocyanate (KW75) as a hardening agent were dissolved in ethyl acetate as a solvent with a solid content of 32 mass %) 31.3 parts by weight, and added Modified polyolefin resin, which is a thermoplastic resin, is dispersed in methylenecyclohexane with a solid content of 20% by mass (modified polyolefin, AP-31Z-EA manufactured by Tanaka (TANAKA) Chemical Co., Ltd.) 450 parts by weight, and amine A solution was prepared so that the ratio of the ethyl formate resin to the modified polyolefin resin would be 10% by mass to 90% by mass as a solid content ratio. At this time, the overall solid content was adjusted to 20% by mass using methylcyclohexane. Then, 71.4 parts by weight of this solution was added with ethyl acetate added to the composite particles obtained in "(2) Preparation of composite particles" in Example 1 to make 10% by mass of a coating solution containing composite particles. 857 parts by weight, and a mixed liquid was prepared so that the ratio of the resin to the composite particles would be 14% by mass to 86% by mass in terms of solid content ratio. At this time, the total solid content was set to 15% by mass using ethyl acetate, and stirred at room temperature for 30 minutes to prepare a coating liquid. Using a bar coater #14, apply the coating solution to the substrate layer so that the weight after drying is 3.5 g/m ² and the dry weight of the adhesive resin is 0.5 g/m ² On the surface of aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) with a thickness of 30 μm, and then heated and dried in an oven at 140°C for 40 seconds to evaporate the solvent, thereby obtaining a primer layer and a functional layer containing composite particles laminate samples.

Example 30 As the adhesive resin, compared with the two-component hardening type urethane resin (which has been mixed with DIC Graphics at a weight ratio of 10:1), which is a thermosetting resin, Polyester polyurethane polyol (LX500) and the company's toluene diisocyanate (KW75) as a hardening agent to make a solid content of 32% by mass and dissolve in ethyl acetate which is a solvent) 156 parts by weight 250 parts by weight of a solution (modified polyolefin, AP-31Z-EA manufactured by TANAKA Chemical Co., Ltd.) dispersed in methylenecyclohexane with a solid content of 20% by mass of a modified polyolefin resin belonging to a thermoplastic resin was added, and A solution was prepared so that the ratio of the urethane resin to the modified polyolefin resin would be 50% by mass to 50% by mass in terms of solid content ratio. At this time, the overall solid content was adjusted to 20% by mass using methylcyclohexane. Then, 71.4 parts by weight of this solution was added with ethyl acetate added to the composite particles obtained in "(2) Preparation of composite particles" in Example 1 to make 10% by mass of a coating solution containing composite particles. 857 parts by weight, and a mixed liquid was prepared so that the ratio of the resin to the composite particles would be 14% by mass to 86% by mass in terms of solid content ratio. At this time, the total solid content was set to 15% by mass using ethyl acetate, and stirred at room temperature for 30 minutes to prepare a coating liquid. Using a bar coater #14, apply the coating solution to the substrate layer so that the weight after drying is 3.5 g/m ² and the dry weight of the adhesive resin is 0.5 g/m ² On the surface of aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) with a thickness of 30 μm, and then heated and dried in an oven at 140°C for 40 seconds to evaporate the solvent, thereby obtaining a primer layer and a functional layer containing composite particles laminate samples.

Example 31 The adhesive resin was mixed with 50 parts by weight of epoxy resin (100% of the main ingredient epoxy resin of adhesive No. 31 manufactured by Daiso (DAISO) Co., Ltd.) and melamine resin ( DIC Graphics (DIC Graphics) TF842 Heat Resistant Reinforcing Agent) 50 parts by weight was made into a solid content of 20% by mass and dissolved in ethyl acetate which is a solvent, and the addition was carried out relative to 71.4 parts by weight Add ethyl acetate to the composite particles prepared in "(2) Prepare composite particles" of Example 1 to make 857 parts by weight of a coating solution containing composite particles at 10% by mass, and use urethane resin and composite particles A mixed liquid was prepared in such a manner that the ratio of solid content was 14% by mass to 86% by mass. At this time, the total solid content was set to 10% by mass using ethyl acetate, and stirred at room temperature for 30 minutes to prepare a coating liquid. Using a bar coater #12, apply the coating solution to the base material layer so that the weight after drying is 3.5 g/m ² and the dry weight of the adhesive resin is 0.5 g/m ² On the surface of aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) with a thickness of 30 μm, and then heated and dried in an oven at 140°C for 40 seconds to evaporate the solvent, thereby obtaining a primer layer containing functional particles and functional Layered laminate samples.

Example 32 The thermosetting resin was used as isocyanate (KW75 toluene diisocyanate manufactured by DIC Graphics was dissolved in ethyl acetate as a solvent with a solid content of 20% by mass), and the relative To its 71.4 parts by weight, 857 parts by weight of a coating solution containing composite particles that has been added to the composite particles obtained in "(2) Preparation of composite particles" in Example 1 by adding ethyl acetate to make 10% by mass, And the mixed liquid was prepared so that the ratio of isocyanate and composite particle|grains might become 14 mass % to 86 mass % in terms of solid content ratio. At this time, the total solid content was set to 10% by mass using ethyl acetate, and stirred at room temperature for 30 minutes to prepare a coating liquid. Using a bar coater #12, apply the coating solution to the base material layer so that the weight after drying is 3.5 g/m ² and the dry weight of the adhesive resin is 0.5 g/m ² On the surface of an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) with a thickness of 30 μm, it was heated and dried in an oven at 140° C. for 40 seconds to evaporate the solvent. Then, the prepared sample was cured at 40° C.×75 RH% for 2 days, and converted into a polyurea resin (urea resin) by reacting isocyanate with moisture in the air. In this way, a laminate sample having a primer layer containing composite particles and a functional layer was prepared.

Example 33 The adhesive resin was made into 100 parts by weight of unsaturated polyester resin (5013PT light-colored transparent FRP resin non-paraffin wax manufactured by PROST) which is a thermosetting resin, and the solid content was 20% by mass. And what is dissolved in ethyl acetate which is a solvent, and relative to 71.4 parts by weight thereof, ethyl acetate is added to the composite particles obtained in "(2) Preparation of composite particles" in Example 1 to set 10 857 parts by mass of the coating liquid containing composite particles was prepared, and a mixed liquid was prepared so that the ratio of the urethane resin to the composite particles would be 14% by mass to 86% by mass in terms of solid content ratio. At this time, the total solid content was set to 10% by mass using ethyl acetate, and stirred at room temperature for 30 minutes to prepare a coating liquid. Using a bar coater #12, apply the coating solution to the base material layer so that the weight after drying is 3.5 g/m ² and the dry weight of the adhesive resin is 0.5 g/m ² On the surface of aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) with a thickness of 30 μm, and then heated and dried in an oven at 140°C for 40 seconds to evaporate the solvent, thereby obtaining a primer layer and a functional layer containing composite particles laminate samples.

Example 34 As an adhesive resin, a two-component hardening type urethane resin (a main agent made by DIC Graphics, which has been blended at a weight ratio of 10:1) is a thermosetting resin. Polyester polyurethane polyol (LX500) and toluene diisocyanate (KW75) of the same company as a hardening agent are dissolved in ethyl acetate which is a solvent with a solid content of 32% by mass) 156 parts by weight, add Ethyl acetate has been added to the composite particles prepared in "(2) Preparation of composite particles" in Example 1 to make 500 parts by weight of a coating solution containing composite particles at 10% by mass, and urethane resin The ratio to the composite particle was prepared to be a mixed liquid so that the ratio of the solid content would be 50% by mass to 50% by mass. 25 parts by weight of polyethylene beads (product name "MIPELON (registered trademark) XM-221U" manufactured by Mitsui Chemicals Co., Ltd., average particle size: 25 μm, melting point: 136° C.) were added to 656 parts by weight of the mixed solution as filling particles, and stirred at room temperature for 30 minutes to prepare a coating liquid. At this time, the total solid content was set to 15% by mass using ethyl acetate, and stirred at room temperature for 30 minutes to prepare a coating liquid. Using a bar coater #18, apply this coating solution to the base material layer so that the weight after drying is 7.5 g/m ² and the dry weight of the adhesive resin is 3.0 g/m ² On the surface of aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) with a thickness of 30 μm, and then heated and dried in an oven at 140°C for 40 seconds to evaporate the solvent, thereby obtaining a primer layer and a functional layer containing composite particles laminate samples.

Example 35 In place of the composite particles in Example 1 (2), hydrophobic particles (product name "AEROSIL R812S" manufactured by EVONIK DEGUSSA, BET specific surface area: 220 m ² /g, primary particle average diameter : 7nm) 5g was dispersed in 100mL of ethanol to prepare a coating liquid, and using a rod coater #16, coated on the surface of the substrate sheet laminated with the primer layer in Example 5, and in an oven at 100 ° C Heat and dry at medium temperature for 40 seconds to evaporate the ethanol, thereby preparing a laminate sample having a substrate layer, a primer layer, and a functional layer in this order. In addition, the target layered amount of the hydrophobic particles was set to 3.0 g/m ² as the weight after drying.

Example 36 Instead of the fluorine-containing composite particles in Example 1 (2), hydrophobic particles (product name "AEROSIL R812S" manufactured by EVONIK DEGUSSA, BET specific surface area: 220m ² /g, primary particles Average diameter: 7nm) 5g was dispersed in 100mL of ethanol to prepare a coating liquid, and using a rod coater #16, coated on the surface of the substrate sheet in Example 1 where the primer layer was laminated, and at 100 ° C Heat and dry in an oven for 40 seconds to evaporate the ethanol, thereby preparing a laminate sample with a substrate layer, a primer layer, and a functional layer in sequence. In addition, the target layered amount of the hydrophobic particles was set to 3.0 g/m ² as the weight after drying.

Example 37 In place of the fluorine-containing composite particles in Example 1 (2), hydrophobic particles (product name "AEROSIL R812S" manufactured by EVONIK DEGUSSA, BET specific surface area: 220 m ² /g, primary particles Average diameter: 7nm) 5g was dispersed in 100mL of ethanol to prepare a coating liquid, and using a rod coater #16, coated on the surface of the substrate sheet laminated with the primer layer in Example 3, and at 100 ° C Heat and dry in an oven for 40 seconds to evaporate the ethanol, thereby preparing a laminate sample with a substrate layer, a primer layer, and a functional layer in sequence. In addition, the target layered amount of the hydrophobic particles was set to 3.0 g/m ² as the weight after drying.

Comparative example 1 Except that the adhesive resin is set to 100 parts by weight of acrylic modified polyolefin resin which is a thermoplastic resin, no thermosetting resin is added, and the proportion of thermosetting resin in the primer layer is set to 0% by mass, no further additions are made to the primer. A laminate sample was obtained in the same manner as in Example 1 except that filler particles were added to the paint liquid.

Comparative example 2 Except that the adhesive resin is set to 100 parts by weight of acrylic modified polyolefin resin which is a thermoplastic resin, no thermosetting resin is added, and the ratio of thermosetting resin in the primer layer is set to 0% by mass, it is set as the same as the implementation. In the same manner as in Example 1, a laminate sample was prepared.

Comparative example 3 Except that the adhesive resin is maleic anhydride-modified polyolefin resin which is a thermoplastic resin (290628-2 manufactured by Tanaka Chemical Co., Ltd. was dissolved in AP-NT solvent manufactured by the same company as a solvent to make a solid content of 20 mass %) 100 parts by weight, no thermosetting resin was added, the ratio of the thermosetting resin in the primer layer was set to 0 mass %, and the base material used for the base sheet was made from aluminum foil to a thickness of 50 μm. A laminate sample was obtained in the same manner as in Example 1 except for chain low-density polyethylene (LLDPE, LIX (registered trademark) film L4102 manufactured by Toyobo Co., Ltd., corona-treated surface).

Comparative example 4 Except that the adhesive resin is 100 parts by weight of butadiene rubber (DAISO Co., Ltd. Adhesive No. 44 for jointing plastics) which is a thermoplastic resin, and the solid content is 20 mass %, which is dissolved in acetic acid which is a solvent. Ethyl ester, no thermosetting resin added, the proportion of thermosetting resin in the primer layer was set to 0% by mass, and the base material used for the base sheet was biaxially stretched polypropylene with a thickness of 20 μm from aluminum foil (P2102 manufactured by Toyobo Co., Ltd., corona-treated surface), a laminate sample was obtained in the same manner as in Example 1.

Comparative Example 5: 71.4 weight of a solution (modified polyolefin, AP-31Z-EA manufactured by TANAKA Chemical Co., Ltd.) dispersed in methylenecyclohexane with a solid content of 20% by mass relative to a modified polyolefin resin which is a thermoplastic resin part, add 857 parts by weight of a coating solution containing composite particles that has been prepared by adding ethyl acetate to 10% by mass of the composite particles prepared in "(2) Modulating Composite Particles" in Example 1, and modify The ratio of the polyolefin to the composite particle was prepared so that the ratio of the solid content was 14% by mass to 86% by mass. At this time, the total solid content was set to 10% by mass using methylcyclohexane, and stirred at room temperature for 30 minutes to prepare a coating liquid. Using a bar coater #12, apply the coating solution to the base material layer so that the weight after drying is 3.5 g/m ² and the dry weight of the adhesive resin is 0.5 g/m ² On the surface of an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) with a thickness of 30 μm, and then heated and dried in an oven at 140° C. for 40 seconds to evaporate the solvent, thereby obtaining a primer layer containing composite particles on the aluminum foil and functional layer laminate samples.

Comparative Example 6 As an adhesive resin, a modified polyolefin resin, which is a thermoplastic resin, was dispersed in a solution of methylcyclohexane at a solid content of 20% by mass (modified polyolefin, AP-31Z manufactured by Tanaka Chemical Co., Ltd. EA) as a coating liquid. Using a bar coater #3, the coating solution was applied to an aluminum foil having a thickness of 30 μm (manufactured by Toyo Aluminum Co., Ltd., 1N30) constituting the base layer so that the weight after drying became 0.5 g/m ² Next, the surface was heated and dried in an oven at 100° C. for 40 seconds to evaporate the solvent, thereby producing a substrate sheet in which a primer layer was laminated on an aluminum foil. Next, 5 g of hydrophobic particles (product name "AEROSIL R812S" manufactured by EVONIK DEGUSSA, BET specific surface area: 220 m ² /g, primary particle average diameter: 7 nm) were dispersed in 100 mL of ethanol to prepare a coating. Cover the liquid, and use a rod coater #18 to apply it on the surface of the aforementioned substrate sheet on which the primer layer is laminated, and heat and dry in an oven at 100°C for 40 seconds to evaporate the ethanol, thereby obtaining the following A sample of a laminate having a substrate layer, a primer layer, and a functional layer. In addition, the target layered amount of the hydrophobic particles was set to 3.0 g/m ² as the weight after drying.

Test Example 1 (Water Repellency Test) (1) Preparation of Measurement Samples For the laminate samples prepared in each of the Examples and Comparative Examples, the functional layer (the exposed surface of the functional particles) was rubbed repeatedly by the following method, A sample for measurement is prepared. Use the friction and wear tester "TRIBOGEAR TYPE: 4.0" manufactured by Shinto Scientific Co., Ltd., and follow the friction coefficient test method stipulated in the Japanese Industrial Standard "JIS K7125: 1999", and implement the friction test by the following method. a) A laminate sample is cut out to a size of 80 mm (width direction)×200 mm (flow direction). b) Fix the cut laminate sample in such a way that the flow direction of the sample will be parallel to the friction and wear direction of the friction and wear testing machine. c) On an ASTM flat indenter with a size of 63.5mm×63.5mm (hereinafter referred to as "indenter"), put a paper towel (made by NIPPON PAPER CRECIA, precision scientific wiping paper (kimwipes)) thick The textured surface is installed so that it will be in contact with the functional layer side of the laminate sample. At this time, as shown in Fig. 4, the paper towel and the indenter will be in close contact, so be careful not to cause wrinkles or the like. d) Install the pressure head of the paper towel on the friction and wear testing machine. At this time, the grain direction of the paper towel is adjusted to be parallel to the direction of friction and wear. e) Adjust the zero balance of the indenter, and set it so that the load on the laminate sample is zero (0g/400cm ² ) when the indenter is parallel to the sample. f) Set a weight of 300g on the indenter, and apply a load of 300g/400cm ² in parallel to the laminate sample, and the paper towel and the functional layer of the above-mentioned laminate sample on the indenter installed with the paper towel have been in contact The friction and wear test was carried out under the state. The friction and wear test was set under the following conditions. a. Friction and wear times: reciprocating 200 times b. Friction and wear speed: 500mm/min c. Movement distance of pressure head during friction and wear: 50mm d. Paper towels will be updated each time in each friction and wear test. After the friction and wear test, gently release the indenter from the laminate sample, taking care not to damage the functional layer of the laminate sample outside the test. In this way, a measurement sample can be prepared. (2) Confirm the water-repellent performance of the test sample on a machine platform inclined at 10 degrees relative to the horizontal plane, so that the surface of the test sample prepared in the above (1) with the functional layer is the upper side, and rub it The direction of wear is perpendicular to the direction of water drop rolling. Near the center of the surface with the functional layer, from a height of 1cm, use a dropper to titrate 30±3g/1 drop of distilled water drop by drop at intervals for a total of 3 times, and pay attention to the place where the water drops will not overlap. In addition, the titration point is carried out within 3 cm of the center of the friction and wear direction of the friction and wear position of the measurement sample prepared in the above (1). The outline of this test method is shown in FIG. 5 . Mark "○" when all three drops of the titrated water drop on the functional layer roll down, and mark "△" when the titrated water drop includes both those that rolled down and those that did not roll down on the functional layer. The case where the 3 drops of the titrated water did not roll off and remained on the functional layer was marked as "×". The results are shown in Tables 1 to 3.

Test example 2 (oil repellency test) (1) Preparation of samples for measurement A measurement sample was prepared in the same manner as in "(1) Preparation of a measurement sample" in Test Example 1 above. (2) Confirm the oil repellency of the test sample On a machine platform inclined at 15 degrees relative to the horizontal plane, the surface of the functional layer of the measurement sample prepared in the above (1) is the upper side, and the direction of friction and wear is perpendicular to the direction of water droplet rolling way to stand still. Near the center of the surface with the functional layer, 30 ± 3 g/ One drop of oil is titrated drop by drop at intervals for a total of 3 times, and care should be taken not to overlap where the oil drops fall. In addition, the titration point is carried out within 3 cm of the center of the friction and wear direction of the friction and wear position of the measurement sample prepared in the above (1). The outline of this test method is shown in FIG. 5 . Mark "○" when all three drops of the titrated oil drop on the functional layer roll off, and mark "△" when the titrated oil drop includes both those that roll off and those that do not roll off on the functional layer ", mark "×" when the 3 drops of the titrated oil drop on the functional layer did not roll off and remained. The results are shown in Tables 1 to 3.

[Table 1]

[Table 2]

[table 3]

It can also be clearly seen from the above results that the laminates of each example can improve durability (sustainability) in terms of water repellency and/or oil repellency, compared to laminates with only thermoplastic resin in the conventional primer layer. In addition, if filler particles are added to the primer layer, the durability of water repellency and/or oil repellency can be further improved. Also, it can be seen that the greater the content of the thermosetting resin in the primer layer, the greater the effect of improving the durability.

10: The laminate of the present invention 11: Substrate layer 12: primer layer 13: Functional layer 13a: Microparticles with water repellency and/or oil repellency 13a': Microparticles with water repellency and/or oil repellency

Fig. 1 is a schematic diagram showing an example of the layer structure of the laminate of the present invention. Fig. 2 is a schematic diagram showing another layer structure example of the laminate of the present invention. Fig. 3 is a schematic diagram showing another layer structure example of the laminate of the present invention. FIG. 4 is a schematic diagram showing the outline of the apparatus for the friction and wear test in Test Examples 1 and 2. FIG. FIG. 5 is a schematic diagram showing the outline of an apparatus for measuring water repellency or oil repellency in Test Examples 1 and 2. FIG.

Symbol Description 10: The laminate of the present invention 11: Substrate layer 12: primer layer 13: Functional layer 13a: Microparticles with water repellency and/or oil repellency 13a': Microparticles with water repellency and/or oil repellency

10: The laminate of the present invention

11: Substrate layer

12: primer layer

13: Functional layer

13a: Microparticles with water repellency and/or oil repellency

13a': Microparticles with water repellency and/or oil repellency

Claims (9)

A laminate, characterized in that it comprises: a) substrate layer; b) primer layer; and c) groups of microparticles with water repellency and/or oil repellency are fixed on the inside and/or surface of the aforementioned primer layer; and (1) The primer layer contains an adhesive resin; (2) Part or all of the adhesive resin is a thermosetting resin; (3) The thermosetting resin contains 5 to 100% by mass in the primer layer; (4) Part or all of the above-mentioned microparticle group forms a functional layer having a three-dimensional network structure, and part or all of the above-mentioned microparticle group is exposed on the outermost surface of the laminate. The laminate according to claim 1, wherein the aforementioned particle groups are exposed in such a manner as to cover substantially all of the outermost surface of the laminate. The laminate according to claim 1, wherein the adhesive resin is present in at least a part of gaps between fine particles of the fine particle group constituting the functional layer. The laminate according to claim 1, wherein the weight ratio [A/(A+B)] of the adhesive resin to the total amount of the adhesive resin (A) and the functional particles (B) is 5 to 97%. The laminate according to claim 1, wherein the primer layer further includes filler particles with an average particle diameter of 0.5 to 100 μm. The laminate according to claim 1, wherein the amount of the primer layer formed is 0.5 to 100 g/m ² based on the solid content of the adhesive resin. The laminate according to claim 1, wherein the formation amount of the aforementioned microparticle group is 0.01 to 100 g/m ² . The laminate according to claim 1, wherein the aforementioned microparticle group is at least one of the following: (a) Composite particles, which have a resin coating layer containing polyfluoroalkyl methacrylate resin on the surface of oxide particles with an average primary particle diameter of 5-50 nm; and (b) Hydrophobic oxide particles with an average primary particle size of 3-100 nm. A method for manufacturing a laminate, which is a method for manufacturing a laminate, and the laminate includes: a) a substrate layer; b) a primer layer; and c) a group of water-repellent and/or oil-repellent fine particles fixed on inside and/or on the surface of the aforementioned primer layer; and The manufacturing method of the laminate is characterized by comprising the following steps: (A) A step of coating a coating liquid for forming a primer layer containing a thermosetting resin on the substrate layer; and coating a group of fine particles containing water repellency and/or oil repellency on the coating film of the above coating liquid the step of dispersion; or (B) A step of applying a coating liquid for forming a primer layer containing water-repellent and/or oil-repellent microparticles and a thermosetting resin to the base layer.