JP7328513B2 - Non-adhesive laminate and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a non-adhesive laminate and its manufacturing method.

Conventionally, in order to impart properties such as weather resistance, impact resistance, water resistance, water repellency, and chemical resistance to the surface of various substrates, it has been widely practiced to form a surface layer containing fluororesin on the substrate surface. It is Examples of methods for forming such a surface layer include a method of coating a fluororesin (Patent Document 1), and a method of forming an underlayer and a fluorine-containing surface layer on the surface of a base material using a powder coating (for example, Patent Document 1). References 2 and 3), and a method of forming a surface layer containing a fluororesin on a substrate surface by coating a composition containing a fluororesin and a specific compound on the substrate surface (Patent Documents 4 and 5). It is

Patent Document 1 discloses a cooked rice hopper, a cooked rice carrying-out device that carries out the cooked rice supplied from the cooked rice hopper while forming it into a substantially plate shape of a predetermined thickness, and a cooked rice cutter that cuts the carried-out cooked rice into a predetermined length. , a rice wrapping plate in which a plurality of rectangular plates are connected to each other so as to be bent into a cylindrical shape, and a drive mechanism for the rice wrapping plate. , wherein at least the surfaces of the cooked rice hopper, the cooked rice unloading device, the cooked rice cutter, and the rice roll wrapping device that come into contact with the rice are each coated with a fluorocarbon resin. It is stated that As a result, sticking of cooked rice is reduced, so that the operation of the device is more stable, and maintenance of the device after use is said to be easier.

In Patent Document 2, a powder coating film is applied to the surface of an aluminum building material by powder coating of a dry blend powder coating of incompatible polyester paint and fluorine paint with different heat melting temperatures. is described. By using such a powder coating, the fluorine coating component is densely distributed on the surface side in the film thickness direction, the polyester coating component is densely distributed on the base side in the film thickness direction, and the glossiness at a measurement angle of 60 ° of 25 to 40% to form a matte surface. Weather resistance is imparted to the surface side of the coating film based on the fluorine paint, impact resistance is imparted to the base side of the coating film based on the polyester paint, and a good appearance is imparted by the matte surface. .

Patent Document 3 describes a powder coating composition containing a specific fluororesin (A1), a specific polyester polymer (B), an isocyanate curing agent and a specific ultraviolet absorber (D) at 170 to 210°C. Baking to form a coating film composed of the melt, reacting the reactive components in the powder coating composition, and then cooling the molten coating film to room temperature to solidify, forming the fluororesin layer and the polyester layer. Forming a cured film having a two-layer structure is described. Such a cured film is said to be excellent in water resistance, chemical resistance and weather resistance.

In Patent Document 4, a dispersion liquid containing fluorinated diamond with a specific particle size distribution is applied to the substrate surface and dried to control the surface parameters of the substrate surface within a specific range, thereby achieving excellent water repellency. It is described that a water-repellent coating film having a

In Patent Document 5, particles of fluororesin having a diameter of several tens of μm or less are mixed to create a porous surface shape in a luminescent paint, and a binder having a methyl group is used as a binder to fix it on a substrate. A super water-repellent surface-emitting sensor is described in which a substrate is coated with a methyl-based silicone having a low cohesive force.

JP-A-10-243775 JP 2012-40503 A Japanese Patent No. 6431765 JP 2016-44092 A JP 2014-6166 A

In the invention described in Patent Document 1, adhesion of cooked rice is prevented by coating the portion that comes into contact with cooked rice with a fluororesin. However, Patent Document 1 does not specify the structure of the coating, and fluororesin generally has low adhesiveness, and common fluororesin coatings are likely to peel off and lack wear resistance and durability. There is In addition, since cooked rice is sticky, there is room for improvement in order to further prevent sticking of cooked rice even with a fluororesin coating. In addition, according to the study of the present inventor, it was found that liquids other than cooked rice, such as water, and powders and slurries containing water may easily adhere in the same way as cooked rice. there is room for improvement.

By using a powder coating as disclosed in Patent Document 2, a coating film having predetermined characteristics can be formed. However, since a dry-blended powder coating with specific components is melted and a matte surface is formed, the surface roughness is too large and there is room for further improvement in suppressing the adhesion of various liquids and powders. There is In addition, since the heat-melting polyester paint and the fluorine paint are incompatible, the layer of the fluorine paint component on the surface tends to separate from the layer of the polyester paint component, and there is a risk of lacking wear resistance and durability.

By using the powder coating composition described in Patent Document 3, the fluororesin layer and the polyester layer can be fixed by chemical bonding. However, in a coating film formed by coating a powder coating composition such as a fluororesin and a polyester polymer in one coat, the fluororesin layer and the polyester layer separate during the melting and curing process of the powder coating composition. Since it forms a two-layer structure, it is presumed to be highly durable, but the fluororesin layer is only formed by layer separation, suppressing the adhesion of various liquids, powders, etc. It is unclear whether

A water-repellent coating film is formed by using the dispersion described in Patent Document 4. However, it is necessary to use a special material, fluorinated diamond. In addition, the fluorinated diamond is likely to separate from the substrate, possibly resulting in poor wear resistance and durability.

Patent document 5 describes a luminescence sensor with a super water-repellent surface that prevents the adhesion of water, ice, and snow, but the fluororesin particles are likely to peel off, and there is a risk of lacking wear resistance and durability. .

As described above, the inventions described in Patent Documents 1 to 3, for example, have room for improvement in preventing adhesion of liquids such as water, powders containing water, slurries, and the like. Moreover, the inventions described in Patent Documents 1, 2, 4, and 5 may lack wear resistance and durability.

Therefore, the object of the present invention is to have a non-adhesive property that can suppress the adhesion of liquids such as water, powders and slurries containing water, etc., even if they have a tendency to adhere easily, and An object of the present invention is to provide a non-adhesive laminate in which peeling of a surface layer containing a fluororesin is suppressed and which is excellent in abrasion resistance. Another object of the present invention is to provide a method for producing a non-adhesive laminate that can easily form such a non-adhesive laminate.

The inventor of the present invention has made intensive studies to solve the problems described above. As a result, the base layer contains a cured product of a specific curable resin composition, the surface layer contains a powdery cured product of a curable fluororesin composition, and the powder of the curable fluororesin composition The inventors have found that the above-mentioned problems can be solved by forming the resulting unevenness on the surface.

A first aspect of the present invention is a non-adhesive laminate having a non-adhesive surface in which a base layer and a surface layer are formed in order on the surface of a base material, and the base layer is a curable resin composition (however, a cured ), the surface layer contains a cured product of a powdery curable fluororesin composition, and is derived from the powder of the curable fluororesin composition The cured product of the curable fluororesin composition is composed of particles derived from the powder, and at least part of the surface of the particles is the curable resin of the underlayer. The present invention relates to a non-adhesive laminate that is fixed in contact with a cured product.

In an embodiment of the present invention, the curable fluororesin composition contains a curable fluororesin and a curing agent, and the cured product of the curable fluororesin composition is crosslinked by the curing agent. It can be a thing.

In an embodiment of the present invention, the surface layer further contains powder of the thermoplastic fluororesin composition, and at least part of the surface of the powder of the thermoplastic fluororesin composition is cured of the curable resin composition of the underlayer. It may have a surface structure in which unevenness derived from powders of the curable fluororesin composition and the thermoplastic fluororesin composition is formed so as to be fixed in contact with an object.

In the embodiment of the present invention, the cured product of the curable resin composition of the underlayer may be a reaction product of a compound having an isocyanate group and a compound having an active hydrogen.

In the embodiment of the present invention, the functional groups contained in the curable resin composition of the underlayer and the functional groups contained in the curable fluororesin composition of the surface layer are chemically bonded to form a cured product of the underlayer and the surface layer. The cured product of may be fixed.

In an embodiment of the present invention, the powder of the curable fluororesin composition may have an average particle size of 50 to 500 μm.

In embodiments of the present invention, the surface layer may have a thickness of 50-1000 μm.

In the embodiment of the present invention, the curable resin composition of the underlayer may be room temperature curable.

In embodiments of the present invention, the underlayer may have a thickness of 0.05 to 10 mm.

The second aspect of the present invention is a method for producing a non-adhesive laminate having a non-adhesive surface in which a base layer and a surface layer are formed in order on the surface of a substrate, wherein the substrate surface is coated with a curable resin composition A step of applying a substance (excluding a curable fluororesin composition) to form a base layer coating film, and before the curable resin composition is completely cured, a powdery substance is applied to the surface of the base layer coating film. A step of applying the curable fluororesin composition to form a surface layer coating, a step of curing the curable resin composition of the underlayer coating, a step of curing the underlayer coating, and a curable fluororesin composition of the surface layer coating It relates to a method for producing a non-adhesive laminate, which includes a surface layer coating film curing step of curing a material, and forms a surface layer having a surface structure in which irregularities derived from the powder of a curable fluororesin composition are formed. .

In an embodiment of the present invention, the curable fluororesin composition contains a curable fluororesin and a curing agent, and the curable fluororesin composition is cured by crosslinking the curable fluororesin with the curing agent. good too.

In an embodiment of the present invention, the curable resin composition of the underlayer coating film may contain a compound having an isocyanate group and an active hydrogen.

In the embodiment of the present invention, the curing of the curable resin composition of the underlayer coating film may be performed by mixing two liquids that are reactive under a room temperature environment.

In the embodiment of the present invention, curing of the curable resin composition of the undercoat layer coating film is performed by mixing a liquid containing a compound having an isocyanate group and a liquid containing an amine, and the isocyanate group and the amine contain After standing still until 95 mol % or more of active hydrogen reacts, the surface layer coating film curing step may be performed.

An embodiment of the present invention may include a step of applying a powdery curable fluororesin composition and a thermoplastic fluororesin composition to the surface of the underlayer coating to form a surface layer coating.

An embodiment of the present invention may include a surface layer coating film curing step of heating and curing the curable fluororesin composition of the surface layer coating film to a temperature lower than the melting point of the thermoplastic fluororesin composition.

According to the present invention, even if liquids such as water, powders containing moisture, and slurries have a tendency to adhere easily, it has a non-adhesive property that can suppress the adhesion, and a fluororesin It is possible to provide a non-adhesive laminate that suppresses peeling of the surface layer containing and has excellent abrasion resistance. Moreover, it is possible to provide a method for producing a non-adhesive laminate that can easily form such a non-adhesive laminate.

A non-adhesive laminate according to an embodiment of the present invention (hereinafter sometimes simply referred to as "laminate") has a base layer and a surface layer formed in order on the surface of a substrate, and the non-adhesive surface have That is, the non-adhesive laminate according to the embodiment has a base material, a base layer and a surface layer, the base layer is formed on the surface of the base material, and the surface layer is formed on the surface of the base layer opposite to the base material. has a structure in which is formed. Also, the outer surface of the surface layer constitutes the non-stick surface. The underlayer contains a cured product of a curable resin composition (excluding a curable fluororesin composition). The surface layer contains a cured product of a powdery curable fluororesin composition and has a surface structure in which irregularities derived from the powder of the curable fluororesin composition are formed. A cured product of the curable fluororesin composition is composed of particles derived from the powder. At least part of the surface of the particles is in contact with and fixed to the cured curable resin of the underlying layer. A boundary region may be formed at the boundary between the base layer and the surface layer, where the cured products of the resin composition constituting each layer are mixed.

In this way, the surface layer has a surface structure in which irregularities derived from the powder of the curable fluororesin composition are formed. By forming an uneven structure, it also has water-repellent properties based on the unevenness, and due to the synergistic effect of these, liquids such as water, powders containing moisture, and slurries tend to adhere easily. However, an excellent non-adhesive effect capable of suppressing the adhesion is exhibited. In addition, at least part of the surface of the particles derived from the powder of the curable fluororesin composition is in contact with and fixed to the curable resin composition of the underlayer, so that the underlayer and the surface layer are well connected. and the peeling of the surface layer is suppressed. Therefore, a non-adhesive laminate having excellent durability can be obtained. In addition, since a curable resin composition is used in the base layer and the surface layer, bonding between the cured resin composition of the base layer and the cured resin composition of the surface layer can be promoted.

The material constituting the base material can be appropriately selected according to the various uses to which the laminate is applied. Such materials include metals such as iron, steel, aluminum, copper, gold, and silver, ceramics, glass, synthetic resins, natural resins, wood, paper, and diamonds. The steel may be any iron alloy that contains carbon in a content of 2.0% or less and may contain other elements, such as stainless steel. Synthetic resins include fiber reinforced resins such as carbon fiber reinforced resins and glass fiber reinforced resins. Among these, stainless steel, aluminum, and iron are preferable from the viewpoint of corrosion resistance, weight, and versatility.

The shape of the substrate is not particularly limited. Examples of the base material include (i) a member constituting the surface of a hopper provided in a conveying machine for conveying raw materials and the like, and (ii) an excavated material such as clay provided in a construction machine such as a bulldozer and an excavator. Materials that make up the surface of the bucket, which is a container for transporting materials and raw materials, (iii) Materials that make up the surface of the vehicle bed provided on dump trucks, etc., (iv) Snowplows, general vehicles (automobiles, railways, etc.) (including), members that make up snow accretion points in ships, houses, bridges, etc., (v) members that make up the surface of gutters, (vi) a sheet that can be applied to the surface of each member of (i) to (v) and the like.

The underlayer contains a cured product of a curable resin composition other than the curable fluororesin composition described later (hereinafter sometimes simply referred to as "curable resin composition"). If necessary, a pretreatment layer may be included to improve the bonding strength between the substrate surface and the cured product. The underlayer is preferably a cured product of a curable resin composition. The resin component of the cured product is generally composed of what is called a thermosetting resin. Thermosetting resins include, for example, phenol resins, amino resins, melamine resins, unsaturated polyester resins, vinyl ester resins, epoxy resins, silicone resins, polyimides, reaction products of compounds having an isocyanate group and compounds having active hydrogen. polymers, etc., which are substances. Among these, from the viewpoint of impact resistance, a polymer that is a reaction product of a compound having an isocyanate group and a compound having an active hydrogen is preferable. The amino resin means a thermosetting resin obtained by an addition condensation reaction between a compound having an amino group (-NH ₂ ) such as urea, melamine, guanamine, aniline, and formaldehyde.

Examples of compounds having an isocyanate group include aromatic isocyanates, alicyclic isocyanates, aliphatic isocyanates, hydrogenated aromatic isocyanates, and the like. More specifically, for example, diisocyanates such as tolylene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), adducts of polyhydric alcohols and diisocyanates ( adduct), isophorone diisocyanate, hexamethylene diisocyanate, and the like. Also, the compound having an isocyanate group may be a blocked isocyanate in which the isocyanate group is temporarily protected with a protective group to render it inactive. The protective group can be removed by heat or the like to regenerate the isocyanate group for use. Examples of protective agents that can serve as protective groups include phenol, caprolactam, oxime, and alcohol.

Compounds having active hydrogen include, for example, polyols, water, amines, urea derivatives, urethane derivatives and the like. Among these, polyols and amines are preferable from the viewpoint of impact resistance. Polyurethane is the reaction product of isocyanates and polyols, and polyurea is the reaction product of isocyanates and amines. Therefore, polyurethane and polyurea are preferable as the thermosetting resin.

Polyols include polyester polyols, polyether polyols, castor oil, and the like. Amines include polyamines and the like. The polyamine may be any compound having two or more amino groups. Amines react more quickly with isocyanates than polyols. Also, the urea bond formed by the reaction between the amino group and the isocyanate group is harder than the urethane bond formed by the reaction between the hydroxyl group and the isocyanate group. Therefore, the compound having active hydrogen is preferably an amine, and more preferably a polyamine. That is, polyurea is more preferable as the thermosetting resin.

The mixing ratio of the compound having an isocyanate group and the compound having an active hydrogen can generally be mixed so that the isocyanate group and the active hydrogen are equimolar. There may be more of either.

The molecular weight of the thermosetting resin can be appropriately determined according to its type and application.

For the curable resin composition, various components such as curable components such as monomers, oligomers, prepolymers, polymers, and curing agents, solvents, and additives necessary for synthesizing the above-mentioned thermosetting resins are appropriately selected. Any composition containing Regarding the solvent, any of solvent-free, organic solvent, water, etc. may be used, but solvent-free is preferable from the viewpoint of environment, safety and workability. In other words, the curable component is preferably one that can be applied to the base material without using a solvent. Examples of thermosetting resins that are reaction products of such curable components include polyurethane, polyurea, and epoxy resins.

The cured product of the curable resin composition can be formed by heat curing, normal temperature curing by mixing predetermined components, normal temperature curing by moisture absorption, etc., depending on the reaction characteristics of the curable components contained in the curable resin composition. Among these, from the viewpoints of heat deterioration prevention and convenience in the process, it is preferable to form by room temperature curing. That is, the curable resin composition is preferably room temperature curable. Thermosetting resins that are reaction products of such curable resin compositions include polyurethane, polyurea, and epoxy resins.

The thickness of the underlayer can be appropriately set according to the application. From the viewpoint of durability, the thickness is preferably 0.05 to 10 mm.

The surface layer contains a cured powdery curable fluororesin composition. A curable fluororesin composition contains a fluororesin having a reactive functional group in the molecule. A curing agent may be included, depending on the nature of the reactive functional groups. Examples of the fluororesin having a reactive functional group in the molecule include (a) a hydroxyl group-containing fluoropolymer described in Japanese Patent No. 6431765; Examples thereof include fluoropolymers having reactive functional groups described in JP-A-5263269.

The hydrogen group-containing fluoropolymer (a) includes units derived from a fluoroolefin, units derived from a monomer having a hydroxyl group that is copolymerizable with the fluoroolefin, and optionally other monomers Examples include those having units derived from the body.

Examples of fluoroolefins include tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene, vinylidene fluoride, and vinyl fluoride.

Examples of monomers having a hydroxyl group include allyl alcohol; hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and cyclohexanediol monovinyl ether; hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether; Vinyl hydroxyalkanoates such as vinyl propionate; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate; 1 type may be sufficient as these and 2 or more types may be contained.

Examples of monomers other than fluoroolefins and hydroxyl group-containing monomers include vinyl monomers such as vinyl ethers, allyl ethers, carboxylic acid vinyl esters, carboxylic acid allyl esters, and olefins. 1 type may be sufficient as these and 2 or more types may be contained.

A commercially available product can be used as such a hydrogen group-containing fluoropolymer. For example, Lumiflon (registered trademark) manufactured by AGC Co., Ltd. may be used. Lumiflon (registered trademark) is an alternating copolymer of fluoroethylene and vinyl ether (FEVE alternating copolymer), and is known as a copolymer containing hydroxyl groups.

The number average molecular weight of the hydroxyl group-containing fluoropolymer is preferably 3,000 to 50,000. The hydroxyl value of the hydroxyl-containing fluoropolymer is preferably 5 to 100 mgKOH/g. The hydroxyl value can be measured according to JIS K 1557-1 (2007 edition).

The fluoropolymer having a reactive functional group (b) has a repeating unit based on tetrafluoroethylene and/or chlorotrifluoroethylene, a dicarboxylic anhydride group, and a polymerizable unsaturated group in the ring. Those containing repeating units based on cyclic hydrocarbon monomers and repeating units based on other monomers, and polymer terminal groups such as ester groups, carbonate groups, hydroxyl groups, carboxyl groups, carbonyl fluoride groups, acid anhydride residues and those having a reactive functional group such as a group. For example, TFE/ _CF2 = _{CFOCF2CF2CF3 /} NAH copolymer, TFE/ _HFP /NAH copolymer, TFE/ _CF2 = _{CFOCF2CF2CF3 / HFP} /NAH copolymer, TFE/VdF /NAH copolymer, TFE/ _CH2 =CH( _CF2 ) _4F /NAH/ethylene copolymer, TFE/ _CH2 =CH( _CF2 ) _2F /NAH/ethylene copolymer, CTFE/ _CH2 =CH( _CF2 ) _4F /NAH/ethylene copolymer, CTFE/ _CH2 =CH( _CF2 ) _2F /NAH/ethylene copolymer, CTFE/ _CH2 =CH( _CF2 ) _2F /NAH / Ethylene copolymers, and those having the above-described reactive functional groups as polymer terminal groups of these copolymers. Here, NAH is 5-norbornene-2,3-dicarboxylic anhydride, HFP is hexafluoropropylene, and VdF is vinylidene fluoride.

Such a fluororesin having a reactive functional group in the molecule is crosslinked by a curing agent having reactivity with the reactive functional group introduced into the fluoropolymer to form a crosslinked product, thereby increasing the reactivity. A cured product of the fluororesin composition is obtained. Examples of curing agents include compounds having an isocyanate group, amine-based curing agents such as melamine resins, guanamine resins, sulfonamide resins, urea resins and aniline resins, β-hydroxyalkylamide-based curing agents, and triglycidyl isocyanurate-based curing agents. etc. As the compound containing an isocyanate group, the compounds described above can be employed. When the fluoropolymer contains a hydrogen group as a reactive functional group, a compound containing an isocyanate group or an amine curing agent can be used. The softening temperature (curing initiation temperature) of the curing agent is preferably 140 to 200°C. Regarding the amount of the curing agent to be added, the molar ratio (A/B) of the reactive functional group (A) in the fluororesin to the reactive functional group (B) in the curing agent is appropriately set according to the surface properties to be imparted. It is possible.

The curable fluororesin composition is powdery. The cured product is also composed of particles derived from the powder of the curable fluororesin composition. For example, a fluororesin having a reactive functional group is in the form of powder, and a cured product can be obtained by a curing reaction while maintaining the particle state. However, it is not necessary that the particles have the same shape before and after the curing reaction. Since the cured product is composed of particles in this way, the surface structure of the surface layer has irregularities derived from the powder. The formation of such unevenness can be controlled by heating conditions and the like. From the viewpoint of imparting better non-adhesiveness to the surface, the average particle size of the powder of the curable fluororesin composition is preferably 50 to 500 μm. The average particle size can be measured, for example, using a laser diffraction/scattering particle size distribution analyzer (Partica LA-960-V2, manufactured by Horiba, Ltd.) or the like.

At least part of the surface of the particles constituting this cured product is in contact with the cured product of the curable resin of the underlying layer and is fixed to the underlying layer. Therefore, detachment of the surface layer is suppressed by suppressing falling off of the particles. In particular, when the functional groups contained in the curable resin composition of the underlayer and the functional groups contained in the curable fluororesin composition of the surface layer are chemically bonded, peeling of the surface layer is further suppressed. . This chemical bond includes bonding between functional groups contained in resin components constituting each resin composition directly or via a curing agent.

The surface layer may further contain powder of a thermoplastic fluororesin composition. As with the powder of the curable fluororesin composition, at least a portion of the surface of the powder is in contact with and fixed to the cured product of the curable resin composition of the underlayer. Further, the powder of the curable fluororesin composition and the cured product of the curable resin composition of the underlayer can be brought into contact with each other and fixed. By including the powder of the thermoplastic resin composition in this way, unevenness derived from the powder of the curable fluororesin composition and the thermoplastic fluororesin composition is formed on the surface of the surface layer. This further improves the non-adhesiveness. The mixing ratio (A/B, weight ratio) of the curable fluororesin composition (A) and the thermoplastic fluororesin composition (B) is preferably 95:5 to 50:50.

The thermoplastic fluororesin constituting the thermoplastic fluororesin composition includes, for example, tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (PFEP), tetra Fluoroethylene-perfluoro(alkyl vinyl ether)-hexafluoropropylene copolymer (EPA), ethylene-tetrafluoroethylene copolymer (PETFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorotri fluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polytetrafluoroethylene (PTFE) and the like. 1 type may be sufficient as these and 2 or more types may be contained.

Various additives may be added to the thermoplastic fluororesin composition as necessary.

The average particle size of the powder of the thermoplastic fluororesin composition is preferably 0.1 to 50 μm from the viewpoint of imparting better non-adhesiveness to the surface.

The thickness of the surface layer can be appropriately set according to the application. From the viewpoint of durability, it is preferably 50 to 1000 μm, more preferably 500 to 1000 μm. Here, the thickness of the surface layer means the sum of the thickness of the surface layer and the aforementioned boundary region. That is, the surface layer is the portion where the cured product of the curable fluororesin composition exists.

The surface layer as described above preferably has a surface roughness (Ra) of 3 to 20 μm. Moreover, the water contact angle of the surface is preferably 120° or more from the viewpoint of exhibiting high water repellency.

A method for producing a non-adhesive laminate according to an embodiment of the present invention is a method for producing a non-adhesive laminate having a non-adhesive surface in which a base layer and a surface layer are sequentially formed on the surface of a substrate, The following steps (1) to (4) are included. The non-adhesive laminate formed through these steps is formed with a surface layer having a surface structure in which irregularities derived from the powder of the curable fluororesin composition are formed. The cured product of the curable fluororesin composition is composed of particles derived from the powder, and at least part of the surface of the particles is in contact with and fixed to the cured product of the curable resin of the underlying layer.

In step (1), a curable resin composition (excluding a curable fluororesin composition) is applied to the substrate surface to form a base layer coating film. As the base material, those described above can be used. If necessary, the surface of the base material may be subjected to cleaning treatment such as degreasing before application to the base material. In addition, if necessary, the surface of the substrate may be subjected to surface treatment such as blasting or etching in order to improve adhesion between the substrate and the underlying layer. As the curable resin composition, those described above can be used. From the viewpoint of impact resistance and workability, the curable resin composition preferably contains a compound having an isocyanate group and active hydrogen. Moreover, from the viewpoint of workability, it is preferable to mix two liquids having reactivity in a room temperature environment. Also from this point of view, it is preferable to contain a compound having an isocyanate group and an active hydrogen. The method of applying the curable resin composition can be appropriately selected according to its form. For example, application with a squeegee or brush, immersion, spray application, and the like can be mentioned. The coating amount can be appropriately determined depending on the properties of the curable resin composition, the application of the non-adhesive laminate, and the like.

In step (2), before the curable resin composition is completely cured, a powdery curable fluororesin composition is applied to the surface of the underlying layer coating to form a surface layer coating. The timing of application may be before the curable resin composition is completely cured. For example, immediately after the start of the reaction, a state in which the reaction has progressed to some extent, and the like. As the powdery curable fluororesin composition, those described above can be used. From the viewpoint of workability and weather resistance, it is preferable to use a curable fluororesin composition and a curing agent, and the curing agent is preferably blocked. By containing the curing agent, the functional group in the curable resin composition of the underlayer, particularly the reactive functional group in the resin component, and the functional group in the curable fluororesin composition, particularly the curable sealing resin It tends to be easily chemically bonded with the reactive functional groups inside. Therefore, the cured product of the base layer and the cured product of the surface layer tend to adhere more firmly. For the coating method, for example, an electrostatic powder coating device can be used. The coating amount may be such that the entire surface of the underlayer coating film is coated.

In a modification, a powdery curable fluororesin composition and a powdery thermoplastic fluororesin composition may be applied. As for the method of application, a mixture of the two may be applied, or separately prepared compositions may be applied simultaneously or in sequence. From the viewpoint of non-adhesiveness and workability, it is preferable to apply a mixture of both.

The coating amount of the powdery curable fluororesin composition can be appropriately determined so that the thickness of the final surface layer is 50 to 1000 μm.

In the underlayer coating film curing step (3), the curable resin composition of the underlayer coating film is cured. For example, before curing the curable fluororesin composition, the curable resin composition of the underlayer coating film is cured. As a result, the particles of the curable fluororesin can be more reliably fixed to the portion in contact with the base layer. Further, for example, it is effective when the components contained in the curable resin composition of the underlayer are decomposed under the curing conditions of the curable fluororesin composition. When the curable resin composition is composed of a polyurea raw material, this raw material may have low heat resistance. When it is necessary to cure the curable fluororesin composition at a temperature higher than this heat resistant temperature, there is a tendency that the polyurea of the underlying layer is not properly formed. On the other hand, since polyurea is a thermosetting resin, by forming polyurea in advance, it is possible to prevent the decomposition of the curable fluororesin composition under the curing conditions and to form a favorable underlayer. Curing of the curable resin composition of the underlayer coating film is performed by selecting a curing method according to the raw material of the resin component contained in the curable resin composition. For example, from the viewpoint of impact resistance and workability, the curing of a curable resin composition is initiated by mixing a liquid containing an isocyanate group and a liquid containing a compound having an active hydrogen to initiate a curing reaction. , is preferably performed. Moreover, from the viewpoint of workability, it is preferable that the curing reaction is initiated by mixing two liquids having reactivity in a room temperature environment. Also from this point of view, it is preferable to contain a compound having an isocyanate group and an active hydrogen. From the viewpoint of reactivity and impact resistance, the compound containing such active hydrogen is preferably an amine, and more preferably a polyamine.

In the surface layer coating film curing step (4), the curable fluororesin composition of the surface layer coating film is cured. For example, after curing the curable resin composition of the underlayer, the curable fluororesin composition is cured. The reason for precuring the curable resin composition of the underlayer is as described in step (3). The conditions for starting the curing of the curable fluororesin composition are when the curing of the curable resin composition of the underlayer coating film is performed by mixing a liquid containing a compound having an isocyanate group and a liquid containing an amine. From the viewpoint of preventing the decomposition of the isocyanate group and the amine and forming a good underlayer, it is preferable that the isocyanate group and the active hydrogen contained in the amine react with each other by 95 mol % or more after standing still. In addition, the active hydrogen contained in the isocyanate group and the amine reacts at 95 mol% or more, which means that when the isocyanate group and the active hydrogen are mixed in equimolar amounts, the lesser one is 95 mol. It means to react more.

When powders of a thermoplastic fluororesin composition and a curable fluororesin composition are used as in the above modification, it is preferable to cure by heating to a temperature lower than the melting point of the thermoplastic fluororesin composition. . As a result, irregularities derived from the powders of the curable fluororesin composition and the thermoplastic fluororesin composition are formed on the surface layer, thereby exhibiting better water repellency and, in turn, exhibiting better non-adhesiveness. can be done.

In the following, the curable resin composition used for forming the underlayer contains a compound having an isocyanate group and an amine, and the curable fluororesin composition used for forming the surface layer is a fluoropolymer containing a hydroxyl group. An embodiment of the method for producing a non-adhesive laminate will be described taking as an example the case where a compound having an isocyanate group blocked with a protective group (also referred to as “blocked isocyanate”) is contained.

As described above, the substrate surface is subjected to cleaning treatment and pretreatment as necessary. Further, a liquid containing a compound having an isocyanate group and a liquid containing an amine are mixed at room temperature to obtain a mixed liquid, and if necessary, defoaming treatment is performed to obtain a curable resin composition. Prepare. Additives can be added as needed. The compound having an isocyanate group is preferably the aforementioned diisocyanate, and the amine is preferably polyamine. The mixing ratio of the isocyanate group-containing compound and the amine is not particularly limited, and generally, the molar ratio (A/B) of the isocyanate group (A) and the active hydrogen (B) contained in the amine is 1. To some extent, but not limited to this. The resulting curable resin composition is applied to the surface of a substrate to form an underlayer coating film. The coating amount can be appropriately determined so that the final thickness of the underlayer is 0.05 to 10 mm. Application can be performed, for example, with a squeegee or the like.

A curable fluororesin composition is prepared as a powdery mixture of a powdery hydroxyl group-containing fluoropolymer and a blocked isocyanate. The mixing ratio of the powdery hydroxyl-containing fluoropolymer and the blocked isocyanate can be appropriately determined according to the types of the hydroxyl-containing fluoropolymer and the blocked isocyanate. The resulting powdery curable fluororesin composition is applied using, for example, an electrostatic powder coating apparatus to form a surface layer coating before the curable resin composition of the underlayer is completely cured. . The reaction between the isocyanate group-containing compound of the underlayer and the amine is initiated by mixing the two liquids, but it takes 0.5 to 24 hours to completely cure under normal temperature conditions. Therefore, it is preferable to apply the powdery curable fluororesin composition, for example, within 10 minutes after the application of the curable resin composition for the underlayer. The powdery curable fluororesin composition may be applied in an amount sufficient to cover the entire surface of the underlayer coating film.

After forming the surface layer coating film, it is allowed to stand in an environment of room temperature to 70° C. for 15 minutes to 24 hours. As a result, the isocyanate group-containing compound reacts with the amine, resulting in complete curing. Both reactions result in the production of polyurea. At this time, the isocyanate groups in the curable resin composition of the underlayer coating react with the hydroxyl groups in the curable fluororesin composition of the surface layer coating to form urethane bonds. As a result, the polyurea of the base layer and the hydrogen group-containing fluoropolymer of the surface layer coating film are interposed through the compound containing the isocyanate group at the contact interface between the base layer coating film and the particles in the surface layer coating film. are bound by chemical bonds. This chemical bond further improves the bonding between the underlying layer and the surface layer.

After curing the underlayer coating film, the substrate on which the underlayer and surface layer coating films are formed is heated to a temperature equal to or higher than the softening temperature (curing initiation temperature) of the blocked isocyanate. The softening temperature can be appropriately determined according to the type of blocked isocyanate, but is preferably 200° C. or less from the viewpoint of preventing thermal deterioration and thermal decomposition of the underlayer. When a powdery thermoplastic fluororesin composition is also used, one having a softening temperature lower than the melting point of the thermoplastic fluororesin composition is used. As a result, the blocked isocyanate groups are regenerated, the hydroxyl groups of the hydrogen group-containing fluoropolymer react with the isocyanate groups to form urethane bonds, the hydroxyl group-containing fluoropolymer is crosslinked, and the cured product is can get. As a result, a surface layer having a surface structure with irregularities derived from the powder of the curable fluororesin composition is formed. Further, when a powdery thermoplastic fluororesin composition is also used, a surface layer having a surface structure in which irregularities derived from the powder of the curable fluororesin composition and the thermoplastic fluororesin composition are formed is formed. be. At this time, the amine may react with the isocyanate group to form a urea bond at the contact interface between the base layer and the particles in the surface layer coating. Further, it is presumed that the particles of the thermoplastic fluororesin composition are physically fixed by the particles derived from the curable fluororesin composition in the surface layer and the underlying layer. The thermoplastic fluororesin composition is particularly preferably PTFE from the viewpoint of improving non-adhesiveness.

The non-adhesive laminate and the method for producing the same according to the embodiments described above can be directly applied to the surface of the substrate composed of the various members shown in (i) to (v) above. That is, these members can be used as the base material, and the underlying layer and the surface layer can be provided. In addition, as shown in (vi) above, a non-adhesive laminate in which a base layer and a surface layer are separately provided on the surface of the base material on the surface of the various members shown in (i) to (v) above. By installing the , even if liquids such as water, powders and slurries containing water tend to adhere to the surface of various members, it gives non-adhesiveness that can suppress the adhesion. can do.

Hereinafter, embodiments of the present invention will be described based on examples.

(Example 1)
A SUS plate (size: 100 mm×100 mm×0.5 mm) made of stainless steel (SUS304) was used as a substrate, and one surface thereof was roughened by file polishing and washed with water. In addition, a curable resin composition (NUKOTE JF-HM, manufactured by NUKOTE Co., Ltd., two-liquid mixed curing type, normal temperature curing type, modified aliphatic polyurea) was prepared. This preparation was carried out by mixing a liquid containing a diisocyanate group and a liquid containing a polyamine, followed by defoaming. In addition, the isocyanate groups and the active hydrogen were mixed so that they were equimolar. The resulting mixed solution was applied to the surface of a SUS plate with a bar coater so as to have a thickness of about 1.0 mm to form a base layer coating film. A powdery curable fluororesin composition (as a curable fluororesin, AGC stock Company product, Lumiflon (registered trademark) LF710F (FEVE alternating copolymer, average particle size: 50 μm, hydroxyl value: 46 mg KOH / g resin) containing isocyanate blocked with ε-caprolactam as a curing agent (curing initiation temperature: 180 ° C)) was applied by an electrostatic powder coating apparatus to a thickness of about 50 μm to form a surface layer coating film.

After forming the surface layer coating film, it is allowed to stand still at room temperature, and the isocyanate group in the diisocyanate in the curable resin composition and the active hydrogen in the polyamine react at 95 mol% or more to form polyurea, and the curable resin composition. Hardened things. After that, the substrate on which each coating film is formed is heated at 180° C. for 15 minutes, and the FEVE alternating copolymer is crosslinked with a curing agent to cure the curable fluororesin composition, and the surface of the substrate is A laminate was obtained in which a base layer, which was a cured product of the curable resin composition, and a surface layer, which was a cured product of the curable fluororesin composition, was formed on the surface of the base layer. The thickness of the laminate was about 1.5 mm. Since the metal substrate has a thickness of 0.5 mm, the total thickness of the surface layer and the base layer was about 1 mm.

(Example 2)
As the curable fluororesin composition, powdery PTFE (TF9207Z, manufactured by 3M, average particle size: 4 μm) was added in 2 parts by weight to 98 parts by weight of the curable fluororesin. to obtain a laminate. The addition amount of the curable fluororesin in Example 1 is 100 parts by weight. As in Example 1, the total thickness of the surface layer and the underlayer was about 1 mm.

(Example 3)
As the curable fluororesin composition, powdery PTFE (TF9207Z, manufactured by 3M, average particle size: 4 μm) was added in 5 parts by weight based on 95 parts by weight of the curable fluororesin. to obtain a laminate. The addition amount of the curable fluororesin in Example 1 is 100 parts by weight. As in Example 1, the total thickness of the surface layer and the underlayer was about 1 mm.

(Example 4)
As the curable fluororesin composition, 10 parts by weight of powdered PTFE (TF9207Z manufactured by 3M, average particle size: 4 μm, melting point: about 327° C.) was added to 90 parts by weight of the curable fluororesin. , to obtain a laminate in the same manner as in Example 1. The addition amount of the curable fluororesin in Example 1 is 100 parts by weight. As in Example 1, the total thickness of the surface layer and the underlayer was about 1 mm.

(Comparative example 1)
A laminate was obtained in the same manner as in Example 1, except that no underlayer was provided. The thickness of the laminate was approximately 0.55 mm.

(Comparative example 2)
A laminate was obtained in the same manner as in Example 1, except that no surface layer was provided. The thickness of the laminate was about 1.5 mm.

(Evaluation 1)
<Measurement of contact angle>
Using the laminates obtained in Examples 1 to 4 and Comparative Examples 1 and 2 as test pieces, the test was performed according to JIS R 3257 by the 1/2θ method. A predetermined amount of purified water (TRUSCO purified water W-20, Trusco Nakayama Co., Ltd.) is placed on the surface of the test piece with a syringe, and within 1 minute, the contact angle measurement device (manufactured by Excima Co., Ltd., SIMage mini7) is used to measure. did.

<Measurement of wear amount>
Using the laminates obtained in Examples 1 to 4 and Comparative Examples 1 and 2 as test pieces, an abrasion resistance test was performed by the abrasive paper method in accordance with JIS K 5600-5-8. The amount of wear was calculated from the weight change before and after the test. The abrasion resistance test was performed using an abrasion tester (Yasuda Seiki Seisakusho Co., Ltd., No. 101-H Taber type abrasion tester) under the following conditions. The weight of the test piece was measured with an electronic balance (MSU125P-100-DI, manufactured by Sartorius Mechatronics Japan KK).

Rotation speed: 60rpm
Load: 4.9N
Abrasion wheel: CS-17
RPM: 500

Table 1 shows the structures of the underlying layers and surface layers of Examples 1 to 4 and Comparative Examples 1 and 2, and the results of "Evaluation 1."

From Table 1, it was confirmed that Examples 1 to 4 had a high contact angle with water, that is, high water repellency. As a result, it can be seen that the non-adhesive laminate of the present invention has a high non-adhesive property against adhering substances such as liquids such as water, powders containing water, slurries, and the like. That is, by sequentially providing a base layer containing a cured product of a curable resin composition and a surface layer of a cured product of a powdery curable fluororesin composition on the substrate surface, the contact angle is large and the non-adhesiveness is excellent. , the amount of wear can be reduced, and a non-adhesive laminate having excellent wear resistance and durability can be obtained by a simple method.

(Example 5)
A SUS plate (size: 100 mm×100 mm×0.5 mm) made of stainless steel (SUS304) was used as a substrate, and one surface thereof was roughened by file polishing and washed with water. In addition, a curable resin composition (Mizeron S-100/A-1000, two-liquid mixed curing type, solvent-free, polyurethane, manufactured by Nippon Paint Anticorrosion Coatings Co., Ltd.) was prepared. This preparation was carried out by mixing a liquid containing a diisocyanate group and a liquid containing a polyol, followed by defoaming. In addition, the isocyanate groups and the active hydrogen were mixed so that they were equimolar. The resulting mixed solution was applied to the surface of a SUS plate with a bar coater so as to have a thickness of about 1.0 mm to form a base layer coating film. A powdery curable fluororesin composition (as a curable fluororesin, AGC stock Company product, Lumiflon (registered trademark) LF710F (FEVE alternating copolymer, average particle size: 50 μm, hydroxyl value: 46 mg KOH / g resin) containing isocyanate blocked with ε-caprolactam as a curing agent (curing initiation temperature: 180 ° C)) was applied by an electrostatic powder coating device to a thickness of about 50 μm to form a surface layer coating film.

After the surface layer coating film is formed, it is allowed to stand still at room temperature, and the isocyanate group in the diisocyanate in the curable resin composition reacts with the active hydrogen in the polyol in an amount of 95 mol% or more to generate polyurethane, and the curable resin composition is formed. Hardened things. After that, the substrate on which each coating film is formed is heated at 180° C. for 15 minutes, and the FEVE alternating copolymer is crosslinked with a curing agent to cure the curable fluororesin composition, and the surface of the substrate is A laminate was obtained in which a base layer, which was a cured product of the curable resin composition, and a surface layer, which was a cured product of the curable fluororesin composition, was formed on the surface of the base layer. The thickness of the laminate was about 1.5 mm. Since the metal substrate has a thickness of 0.5 mm, the total thickness of the surface layer and the base layer was about 1 mm.

(Example 6)
As the curable fluororesin composition, powdery PTFE (TF9207Z, manufactured by 3M, average particle size: 4 μm) was added in an amount of 10 parts by weight based on 90 parts by weight of the curable fluororesin. to obtain a laminate. The amount of the curable fluororesin added in Example 5 is 100 parts by weight. As in Example 5, the total thickness of the surface layer and the underlayer was about 1 mm.

(Example 7)
In the same manner as in Example 1, a laminate in which a base layer, which is a cured product of a curable resin composition, is formed on the surface of a base material, and a surface layer, which is a cured product of a curable fluororesin composition, is formed on the surface of the base layer. got As in Example 1, the total thickness of the surface layer and the underlayer was about 1 mm.

(Example 8)
In the same manner as in Example 4, a laminate in which a base layer, which is a cured product of a curable resin composition, is formed on the surface of a base material, and a surface layer, which is a cured product of a curable fluororesin composition, is formed on the surface of the base layer. got As in Example 4, the total thickness of the surface layer and the underlayer was about 1 mm.

(Comparative Example 3)
A laminate was obtained in the same manner as in Example 5, except that no underlayer was provided. The thickness of the laminate was approximately 0.55 mm.

(Comparative Example 4)
A laminate was obtained in the same manner as in Example 6, except that no underlayer was provided. The thickness of the laminate was approximately 0.55 mm.

(Evaluation 2)
<Micro slurry jet erosion (MSE) test>
Measured using an MSE tester (N-MSE-A) manufactured by Parmeso Co., Ltd. Table 2 shows the measurement conditions of the apparatus.

The erosion depth (μm) when a predetermined amount of slurry containing the above particles and water is collided eight times against the surface of the laminate of Examples 5 to 8 and Comparative Example 3 and the total amount of particles projected at that time MSE Resistance values (erosion rate, projection amount/depth, g/μm) were calculated. The MSE resistance value is a value that serves as an index of erosion wear, and when spherical alumina particles are used, it is said that the greater the value, the higher the impact fatigue resistance.

<Tape peeling test>
Laminates of Examples 5 to 8 and Comparative Examples 3 and 4 with a size of 300 mm × 100 mm × 2 mm were prepared, and a 24 mm wide adhesive tape (Nichiban Co., Ltd. (manufactured by Shimadzu Corporation, Cellotape (registered trademark) No. 405) was attached, and the peel strength was measured by a 180° peeling method using a tensile tester (manufactured by Shimadzu Corporation, Autograph AG-20kNX, 1kN load cell). The tensile speed was set to 5 mm/sec.

<Measurement of contact angle>
Using the laminates obtained in Examples 5 to 8 and Comparative Examples 3 and 4, contact angles were measured in the same manner as in Evaluation 1.

Table 3 shows the structures of the underlying layers and surface layers of Examples 5 to 8 and Comparative Examples 3 and 4 and the results of "Evaluation 2".

As shown in Table 3, compared to Comparative Examples 3 and 4, Examples 5 to 8 have a high contact angle with water, that is, high water repellency, and have good properties against erosion wear. was confirmed. Therefore, by sequentially providing a base layer containing a cured product of a curable resin composition and a surface layer of a cured product of a powdery curable fluororesin composition on the substrate surface, the contact angle is large and the non-adhesiveness is excellent. , the amount of wear can be reduced, and a non-adhesive laminate having excellent wear resistance and durability can be obtained by a simple method.

In addition, since the MSE resistance value of Comparative Example 4 is extremely lower than that of Comparative Example 3, Comparative Example 4 has improved wear resistance and durability by adding an additive with low adhesion such as PTFE. It can be seen that the sex has decreased. On the other hand, when comparing Comparative Example 4 with Examples 6 and 8, the MSE resistance values of Examples 6 and 8 are sufficiently larger than those of Comparative Example 4. In No. 8, by forming the underlayer, even when PTFE is added, it can be seen that wear resistance and durability characteristics are exhibited.

Claims (15)

A non-adhesive laminate having a non-adhesive surface in which a base layer and a surface layer are sequentially formed on the surface of a substrate,
The underlayer contains a cured product of a curable resin composition (excluding a curable fluororesin composition),
The surface layer contains a cured product of a powdery curable fluororesin composition and has a surface structure in which irregularities derived from the powder of the curable fluororesin composition are formed,
The cured product of the curable fluororesin composition is composed of particles derived from the powder, and at least a part of the surface of the particles is in contact with and fixed to the cured product of the curable resin of the underlying layer ,
The functional groups contained in the curable resin composition of the base layer and the functional groups contained in the curable fluororesin composition of the surface layer are chemically bonded, and the cured product of the base layer and the cured product of the surface layer are fixed. non -stick laminate. The curable fluororesin composition contains a curable fluororesin and a curing agent,
2. The non-adhesive laminate according to claim 1, wherein the cured product of the curable fluororesin composition is a crosslinked product of the curable fluororesin crosslinked by the curing agent. The surface layer further contains powder of the thermoplastic fluororesin composition, and at least a part of the surface of the powder of the thermoplastic fluororesin composition is in contact with and fixed to the cured product of the curable resin composition of the underlayer, 3. The non-adhesive laminate according to claim 1 or 2, having a surface structure in which irregularities derived from powders of the curable fluororesin composition and the thermoplastic fluororesin composition are formed. The non-adhesive laminate according to any one of claims 1 to 3, wherein the cured product of the curable resin composition of the underlayer is a reaction product of a compound having an isocyanate group and a compound having an active hydrogen. . The non-adhesive laminate according to any one of claims 1 to 4 , wherein the powder of the curable fluororesin composition has an average particle size of 50 to 500 µm. The non-adhesive laminate according to any one of claims 1 to 5 , wherein the surface layer has a thickness of 50 to 1000 µm. The non-adhesive laminate according to any one of claims 1 to 6 , wherein the curable resin composition of the underlayer is room temperature curable. The non-adhesive laminate according to any one of claims 1 to 7, wherein the underlayer has a thickness of 0.05 to 10 mm. A method for producing a non-adhesive laminate having a non-adhesive surface in which a base layer and a surface layer are sequentially formed on the surface of a base material,
A step of applying a curable resin composition (excluding a curable fluororesin composition) to the substrate surface to form a base layer coating film;
A step of applying a powdery curable fluororesin composition to the surface of the underlying layer coating before the curable resin composition is completely cured to form a surface layer coating;
Underlayer coating film curing step for curing the curable resin composition of the underlayer coating film,
A surface layer coating film curing step for curing the curable fluororesin composition of the surface layer coating film,
including
The functional groups contained in the curable resin composition of the base layer and the functional groups contained in the curable fluororesin composition of the surface layer are chemically bonded, and the cured product of the base layer and the cured product of the surface layer are fixed. 3. A method for producing a non-adhesive laminate, comprising forming a surface layer having a surface structure in which irregularities derived from powder of a curable fluororesin composition are formed. 10. The non-adhesive composition according to claim 9 , wherein the curable fluororesin composition contains a curable fluororesin and a curing agent, and the curable fluororesin composition is cured by cross-linking the curable fluororesin with the curing agent. A method for producing a flexible laminate. The method for producing a non-adhesive laminate according to claim 9 or 10 , wherein the curable resin composition of the base layer coating film contains a compound having an isocyanate group and an active hydrogen. The non-adhesive laminate according to any one of claims 9 to 11 , wherein the curing of the curable resin composition of the underlayer coating film is performed by mixing two liquids having reactivity in a room temperature environment. manufacturing method. Curing of the curable resin composition of the underlayer coating film is performed by mixing a liquid containing a compound having an isocyanate group and a liquid containing an amine, and the active hydrogen contained in the isocyanate group and the amine reacts at 95 mol% or more. 13. The method for producing a non-adhesive laminate according to any one of claims 9 to 12 , wherein the surface layer coating film curing step is performed after the surface layer coating film is cured. 14. The method according to any one of claims 9 to 13 , comprising the step of forming a surface layer coating film by applying a powdery curable fluororesin composition and a thermoplastic fluororesin composition to the surface of the undercoat layer coating film. The method for producing the non-adhesive laminate according to 1. 15. The non-adhesive laminate according to claim 14 , further comprising a step of curing the surface layer coating film by heating the curable fluororesin composition of the surface layer coating film to a temperature lower than the melting point of the thermoplastic fluororesin composition. manufacturing method.