Structure provided with non-adhesive functional film and method for producing structure

Abstract

To form a concavo-convex structure on a surface of a structure having a non-adhesive functional film while preventing deformation of a substrate.SOLUTION: A structure according to an aspect of the present invention comprises: a substrate; a composite film provided on a surface of the substrate; and a non-adhesive functional film provided on a surface of the composite film. The composite film includes a plurality of cellulose nanocrystal aggregates and a coating layer composed of an organic-inorganic hybrid glass that covers the plurality of cellulose nanocrystal aggregates.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The disclosure herein relates to a structure provided with a non-stick functional film and a method for manufacturing the structure. [Background technology]

[0002] Structures having a non-adhesive functional film are known, and the non-adhesive functional film is applied to various articles such as molds, foods, packaging materials, office equipment, printing parts, and transportation equipment.

[0003] A conventional structure equipped with a non-adhesive functional film is described in Japanese Patent Laid-Open Publication No. 2016-210190 (Patent Document 1). The structure described in Patent Document 1 includes a substrate having an uneven surface structure and a functional film provided on the surface of the substrate. A non-adhesive high polymer such as a silicone resin is used as the material for the functional film. The surface of the substrate is roughened by blasting, resulting in an uneven structure. In this structure, the uneven structure on the substrate surface reduces the contact area between the substrate surface and an adhesive substance, and the substrate surface is provided with a functional film made of a non-adhesive high polymer with low surface free energy, thereby suppressing adhesion of other substances to the substrate surface. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-210190 Summary of the Invention [Problem to be solved by the invention]

[0005] In conventional structures equipped with non-adhesive functional films, the uneven structure on the substrate surface is formed by abrasive processing such as blasting. Depending on the shape of the substrate, it is not possible to project an abrasive onto some areas of the substrate surface, and an uneven structure cannot be formed in these areas where the abrasive cannot be projected. In addition, the substrate is deformed when the abrasive collides with the substrate surface, and forming an uneven structure on the substrate surface may result in the product dimensions not meeting specifications. Furthermore, if the substrate has low hardness, the uneven structure on the substrate surface is likely to be flattened by friction and impact applied to the structure during use or in later manufacturing processes, and the non-adhesive functional film provided on the uneven structure is also likely to be lost.

[0006] An object of the inventions disclosed in this specification is to solve or alleviate at least some of the problems of the prior art described above. The various inventions disclosed in this specification are collectively referred to as "the present invention." One specific object of the present invention is to form a relief structure on the surface of a structure having a non-adhesive functional film without deforming the substrate. One specific object of the present invention is to improve the durability of the relief structure formed on the surface of a structure. Objects of the present invention other than those described above will become clear throughout the entire specification. The inventions disclosed in this specification may also solve problems that are understood from other than those described in the "Problem to be Solved by the Invention" section. [Means for solving the problem]

[0007] A structure according to one aspect of the present invention comprises a substrate, a composite membrane provided on the surface of the substrate, and a non-adhesive functional membrane provided on the surface of the composite membrane. The composite membrane includes a plurality of cellulose nanocrystal aggregates and a coating layer made of organic-inorganic hybrid glass covering the plurality of cellulose nanocrystal aggregates. [Effects of the Invention]

[0008] According to one aspect of the present invention, a relief structure can be formed on the surface of a structure having a non-adhesive functional film without deforming the substrate. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a cross-sectional view that schematically shows a portion of a cross section of a structure 1 according to one embodiment of the present invention. [Figure 2] FIG. 10 is a cross-sectional view schematically showing a part of a cross section of a structure 51 according to another embodiment of the present invention. [Figure 3] FIG. 10 is a cross-sectional view schematically showing a part of a cross section of a structure 61 according to yet another embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] A structure according to one aspect of the present invention comprises a substrate, a composite film disposed on the surface of the substrate, and a functional film disposed on the surface of the composite film. The composite film includes a plurality of cellulose nanocrystal aggregates and a coating layer made of organic-inorganic hybrid glass disposed so as to cover the plurality of cellulose nanocrystal aggregates. The cellulose nanocrystal aggregates are deposited on the surface of the substrate. The height of the cellulose nanocrystal aggregates varies at different positions on the surface of the substrate depending on the particle size and orientation of the cellulose nanocrystal aggregates. The surface of the composite film has an uneven structure due to the difference in height of the cellulose nanocrystal aggregates from the surface of the substrate. The functional film contains a non-adhesive material with low surface free energy. The surface of the functional film also has an uneven structure formed in a shape that matches the uneven structure of the underlying composite film. In one aspect, the functional film is disposed on the outermost layer of the structure.

[0011] In a structure constructed in this manner, the non-adhesive functional film with a textured surface inhibits adhesion of other substances to the surface. The textured structure on the functional film's surface is not produced by processing the substrate surface, but by multiple cellulose nanocrystal aggregates provided on the substrate surface. This allows the textured structure to be formed on the surface of the structure without deforming the substrate surface. Furthermore, in the composite film, the highly flexible cellulose nanocrystal aggregates are covered with a coating layer made of a hard organic-inorganic hybrid glass. This composite layer combines flexibility with high hardness, resulting in high fracture resistance. Therefore, the textured structure formed on the surface of the structure has high durability.

[0012] Because the adhesion of other substances to the surface of a structure to which the present invention is applied is suppressed, the present invention can be used in a variety of products and applications in which suppression of adhesion of other substances is desired. For example, the structure of the present invention can be used as a component or part of various industrial products, such as molding dies, packaging materials, office equipment, printing parts, and transportation equipment. The present invention can also be applied to agricultural products such as vegetables and fruits. The uses of the structure explicitly described in this specification are merely examples, and the structure of the present invention can be used in a variety of applications not explicitly described in this specification.

[0013] Various embodiments of the present invention will be described below with appropriate reference to the drawings. Components common to multiple drawings are designated by the same or similar reference numerals throughout the drawings. Please note that the drawings are not necessarily drawn to scale for the sake of convenience. The embodiments described below do not necessarily limit the invention according to the claims. Elements described in the following embodiments are not necessarily essential to the solution of the invention.

[0014] 1 First embodiment (structure 1) A structure 1 according to a first embodiment of the present invention will be described with reference to Fig. 1. Fig. 1 is a cross-sectional view schematically showing a portion of a cross section of the structure 1. As shown in Fig. 1, the structure 1 includes a substrate 11, a composite film 12 provided on the surface of the substrate 11, and a functional film 13 provided on the surface of the composite film 12.

[0015] 1-1 Base material 11 The material of the substrate 11 is selected depending on the intended use of the structure 1. Examples of the material of the substrate 11 include metal, metal oxide, ceramic, and synthetic resin. More specifically, the material of the substrate 11 may be stainless steel such as SUS304, bearing tool steel such as SKD, cemented carbide such as tungsten carbide, steel, soft metals such as titanium, magnesium, and aluminum, or alloys thereof, metal oxides such as alumina, zirconia, and titania, ceramics such as tiles, resins such as polyester, engineering plastics such as Ultem, carbon fiber materials, silk, cotton, wool, or blends thereof, or semiconductor materials such as silicon. The material of the substrate 11 is not limited to those exemplified in this specification. The substrate 11 may also be agricultural products such as vegetables and fruits. The shape and dimensions of the substrate 11 are determined appropriately depending on the intended use of the structure 1.

[0016] As will be described later, the composite film 12 and the functional film 13 provided on the surface of the substrate 11 can be formed at room temperature, so the substrate 11 may be made of a material with low heat resistance, such as plastic or wood.

[0017] 1-2 Composite membrane 12 Composite film 12 is provided on the surface of substrate 11. Composite film 12 includes a plurality of cellulose nanocrystal aggregates 12a and coating layer 12b that covers cellulose nanocrystal aggregates 12a.

[0018] The cellulose nanocrystal aggregate 12a is formed by aggregating multiple cellulose nanocrystals. As known to those skilled in the art, cellulose nanocrystals can be obtained by hydrolyzing cellulose fibers with acid to obtain fine cellulose fibrous material in which the amorphous regions of the cellulose fibers are cut, and then subjecting this fine cellulose fibrous material to a defibration treatment. The cellulose nanocrystal aggregate 12a contained in the composite film 12 is obtained by aggregating such cellulose nanocrystals. As described below, the composite film 12 containing the cellulose nanocrystal aggregate 12a is applied from a raw material solution in which powdered cellulose nanocrystal aggregates and other raw materials are dissolved in an organic solvent such as alcohol. The volume-based average particle size (D50) of the cellulose nanocrystal aggregate is preferably 0.1 to 10 μm. The volume-based average particle size of the cellulose nanocrystal aggregate is measured by a laser diffraction / scattering method in accordance with JIS Z 8825. The cellulose nanocrystal aggregates 12a contained in the composite membrane 12 are cellulose nanocrystal aggregates in the raw solution that have been fixed to the surface of the substrate 11, and therefore the volume-based average particle size (D50) of the cellulose nanocrystal aggregates added to the raw solution can be set to the average particle size of the cellulose nanocrystal aggregates 12a in the peritoneal membrane 12a. The cellulose nanocrystal aggregates used in one embodiment of the present invention may be produced by grinding crystalline biofibers in a low-dielectric-constant organic solvent such as toluene, as described in, for example, JP 2016-221425 A.

[0019] Coating layer 12b is made of organic-inorganic hybrid glass. Organic-inorganic hybrid glass is produced by hydrolyzing a raw material containing alkoxide to produce a hydrolyzate, and then subjecting this hydrolyzate to a dehydration condensation reaction. Coating layer 12b contains siloxane converted from the raw alkoxide. As described above, coating layer 12b covers cellulose nanocrystal aggregates 12a. The siloxane contained in coating layer 12b is chemically bonded to cellulose nanocrystal aggregates 12a.

[0020] Composite film 12 is formed by a sol-gel process using a raw material solution containing powdered cellulose nanocrystal aggregates and alkoxysilane. More specifically, composite film 12 is formed by applying the raw material solution containing cellulose nanocrystal aggregates and alkoxysilane to the surface of substrate 11, hydrolyzing the alkoxysilane in the raw material solution applied to the surface of substrate 11 to produce a hydrolyzate, and then dehydrating and condensing this hydrolyzate.

[0021] The raw material solution can be obtained, for example, by dissolving alkoxysilane-containing silicone in an organic solvent such as alcohol to prepare a mixed solution, and then dispersing powdered cellulose nanocrystal aggregates in this mixed solution. The cellulose nanocrystal aggregates are added, for example, so that the ratio of cellulose nanocrystals to 100 wt% of the mixed solution is 5 wt% to 15 wt%. As described above, the volume-based average particle size (D50) of the cellulose nanocrystal aggregates is, for example, 0.1 to 10 μm. Because functional groups such as hydroxyl groups and carboxyl groups are present on the surface of the cellulose nanocrystals, the cellulose nanocrystal aggregates can be dispersed in an organic solvent without the use of a dispersant. Dispersing the cellulose nanocrystal aggregates in an organic solvent without the use of a dispersant prevents the surface of the cellulose nanocrystal aggregates from being covered with the dispersant, which facilitates chemical bonding between the functional groups present on the surface of the cellulose nanocrystal aggregates 12a and the siloxane contained in the coating layer 12b in the composite film 12.

[0022] The raw material solution is thinly applied to the surface of the substrate 11. The raw material solution applied to the surface of the substrate 11 is preferably diluted with alcohol so that the thickness of the composite film 12 is as thin as about 100 to 1000 nm.

[0023] Examples of alkoxysilanes that can be used in the mixed solution include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), and polymers thereof. The alkoxysilanes that can be used in the raw material solution are not limited to those explicitly mentioned in this specification.

[0024] As described above, an alcohol can be used as the organic solvent to dissolve the raw material. Examples of the alcohol used as the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 1,1-dimethyl-1-ethanol, and other known alcohols.

[0025] In the composite film 12 obtained by curing the raw material solution, at least some of the cellulose nanocrystal aggregates 12a are in direct contact with the surface of the substrate 11, as shown in Figure 1. In addition, some of the cellulose nanocrystal aggregates 12a may be arranged so that they are stacked on top of other cellulose nanocrystal aggregates 12a. Furthermore, because the cellulose nanocrystal aggregates 12a are formed by the aggregation of needle-shaped cellulose nanocrystals, the surface of each cellulose nanocrystal aggregate 12a also has numerous irregularities.

[0026] As described above, composite film 12 is formed by applying a raw material solution containing cellulose nanocrystal aggregates to the surface of substrate 11 and then curing the raw material solution. Therefore, a textured structure resulting from cellulose nanocrystal aggregates 12a deposited on the surface of substrate 11 appears on the surface of composite film 12. As shown in FIG. 1 , the height of cellulose nanocrystal aggregates 12a from the surface of substrate 11 varies depending on the position on the surface of substrate 11 due to differences in particle size of cellulose nanocrystal aggregates 12a and differences in the orientation of cellulose nanocrystal aggregates 12a on the surface of substrate 11. Because the height of cellulose nanocrystal aggregates 12a varies depending on the position on the surface of substrate 11, a textured shape is formed on the surface of composite film 12 that follows the difference in height of cellulose nanocrystal aggregates 12a (i.e., the textured shape). As described below, a textured structure that follows the textured shape of the surface of composite film 12 is also formed on the surface of functional film 13. Therefore, a textured structure that follows the textured structure of composite film 12 also appears on the outermost layer of structure 1. In this way, since the outermost layer of structure 1 has an uneven structure, the contact area with other substances that come into contact with the surface of structure 1 can be reduced, and adhesion of other substances to the surface of structure 1 can be suppressed.

[0027] In one embodiment of the present invention, the thickness of coating layer 12b is thinner than the average particle size of cellulose nanocrystal aggregates 12a. By making the thickness of coating layer 12b thinner than the average particle size of cellulose nanocrystal aggregates 12a, the unevenness of cellulose nanocrystal aggregates 12a is more easily reflected in the surface shape of composite film 12. In other words, by making the thickness of coating layer 12b thinner than the average particle size of cellulose nanocrystal aggregates 12a, the unevenness of the surface of coating layer 12b can be increased. By increasing the unevenness of the surface of coating layer 12b, the non-adhesive properties of structure 1 can be improved.

[0028] The cellulose nanocrystal aggregates 12a, formed by the aggregation of fibrous cellulose nanocrystals, have high flexibility. On the other hand, the coating layer 12b, made of organic-inorganic hybrid glass, is hard and crack-resistant. Therefore, the composite film 12, which is a composite material of the highly flexible cellulose nanocrystal aggregates 12a and the coating layer 12b made of hard organic-inorganic hybrid glass, has both high flexibility and high hardness. The high flexibility and high hardness of the composite film 12 can improve the fracture resistance of the composite film 12.

[0029] The sol-gel reaction for forming the composite film 12 from the raw material solution proceeds even at room temperature (for example, 25° C.), so the composite film 12 can be formed even on the surface of a substrate 11 with low heat resistance.

[0030] The composite film 12 is formed by curing a raw material solution applied to the substrate 11, and therefore, a concave-convex structure can be formed on the surface of the structure 1 without changing the shape of the surface of the substrate 11. For this reason, the composite film 12 is particularly suitable for structures 1 that require high dimensional accuracy.

[0031] 1-3 Functional membranes 13 A non-adhesive functional film 13 is provided on the surface of the composite film 12. The functional film 13 is, for example, a coating film having water-repellent properties. In one embodiment, the functional film 13 has a thickness of 1 nm to 10 nm. As described above, because the functional film 13 is thin, an uneven shape that follows the uneven structure formed on the surface of the composite film 12 appears on the surface of the functional film 13. In other words, an uneven structure having a shape that follows the uneven structure on the surface of the composite film 12 is formed on the surface of the functional film 13.

[0032] The functional film 13 contains a compound with molecules having low surface free energy to provide non-adhesive properties. In one embodiment of the present invention, the compound with molecules having low surface free energy contained in the functional film 13 is, for example, at least one compound selected from the group consisting of fluorine compounds, hydrocarbon compounds, and silicone resins. The compound with molecules having low surface free energy contained in the functional film 13 is not limited to those specifically mentioned in this specification.

[0033] The functional film 13 contains a compound whose molecules have low surface free energy, and has an uneven structure formed on its surface, so that the functional film 13 can impart high non-adhesiveness to the surface of the structure 1.

[0034] The functional film 13 may be a self-assembled monolayer (SAM) of molecules with low surface free energy. As known to those skilled in the art, a self-assembled monolayer is a monolayer in which molecules are aligned. One end of the self-assembled monolayer constituting the functional film 13 is adsorbed to the composite film 12 (specifically, the coating layer 12b), and the other end is exposed on the surface of the functional film 13. The self-assembled monolayer constituting the functional film 13 may have a bonding functional group at a first end on the side adsorbed to the coating layer 12b, which chemically bonds to the organic-inorganic hybrid glass constituting the coating layer 12b. This bonding functional group may be a hydroxyl group or a carboxyl group. The hydroxyl group or the carboxyl group chemically bonds to the siloxane contained in the coating layer 12b made of the organic-inorganic hybrid glass. The self-assembled monolayer constituting the functional film 13 may have a water-repellent functional group at a second end opposite the first end. The water-repellent functional group may be, for example, an alkyl group, a saturated fluoroalkyl group, a dimethylsiloxy group, or a trimethylsiloxy group. The functional groups present at the first end and the second end of the self-assembled monolayer constituting the functional film 13 are not limited to those specifically mentioned in this specification.

[0035] The surface of the functional film 13 has an uneven structure, which increases the surface area of ​​the functional film 13. Therefore, the surface of the functional film 13 can exhibit better non-adhesive properties than a film with a flat surface.

[0036] The structure 1 may include components other than those shown in Fig. 1. For example, an intermediate film may be provided between the composite film 12 and the functional film 13. This intermediate film may be a thin film made of organic-inorganic hybrid glass, similar to the coating layer 12b.

[0037] In addition to the organic-inorganic hybrid glass, the composite film 12 may contain particles for exhibiting antibacterial properties, water repellency, or other functions. Like the composite film, the interlayer film made of organic-inorganic hybrid glass can also contain particles for exhibiting functions.

[0038] 1-4 Manufacturing method of structure 1 Next, an example of a method for manufacturing the structure 1 will be described. First, a substrate 11 appropriate for the intended use is prepared. Next, a raw material solution containing cellulose nanocrystal aggregates and alkoxysilane is applied to the surface of the substrate 11. This raw material solution is cured to form a composite film 12 on the surface of the substrate 11. The substrate 11 to which the raw material solution has been applied is left, for example, in an environment at room temperature and a relative humidity of 60% for one to five days to promote a dehydration-condensation reaction. In the raw material solution applied to the surface of the substrate 11, the alkoxysilane is hydrolyzed to produce a hydrolyzate, which then undergoes dehydration-condensation to produce organic-inorganic hybrid glass. This organic-inorganic hybrid glass covers the cellulose nanocrystal aggregates contained in the raw material solution. In this way, a composite film 12 is formed on the surface of the substrate 11, comprising cellulose nanocrystal aggregates 12a and a coating layer 12b made of organic-inorganic hybrid glass.

[0039] Next, a raw material solution containing organic molecules is applied to the surface of the composite film 12, thereby forming a functional film 13 on the surface of the composite film 12. The functional film 13 may be a self-assembled monolayer formed by self-assembly of organic molecules. Examples of organic molecule solutions used to form the functional film 13 include a PFPE solution containing PFPE (perfluoropolyether) with alkoxysilane at a concentration of 0.1 wt% to 0.5 wt%, a hydrocarbon solution in which a hydrocarbon with alkoxysilane is dissolved at a concentration of 0.1 wt% to 0.5 wt% in a 1:1 mixture of xylene and toluene, or a silicone solution in which a silicone coating agent such as an isocyanate silane compound is diluted with ethyl acetate. The intermediate formed by applying the raw material solution containing organic molecules to the surface of the composite film 12 is left for one to five days, for example, in an environment at room temperature and a relative humidity of 60% to promote self-assembly of the organic molecules. The self-assembly of the organic molecules on the surface of the composite film 12 forms the functional film 13, which is a self-assembled monolayer or thin film of the organic molecules. When a PFPE solution is applied to the surface of the composite film 12, a self-assembled monolayer of a fluorine compound having a perfluoropolyether group in its main chain is formed on the surface of the composite film 12 due to self-organization of the perfluoropolyether. When a hydrocarbon solution is applied to the surface of the composite film 12, a self-assembled monolayer of a hydrocarbon compound is formed on the surface of the composite film 12. When a silicone solution is applied to the surface of the composite film 12, a thin film of a silicone resin having a siloxane bond in its main chain is formed on the surface of the composite film 12.

[0040] In this manner, a structure 1 including the substrate 11, the composite film 12 provided on the surface of the substrate 11, and the functional film 13 provided on the surface of the composite film 12 is obtained.

[0041] 2 Second embodiment (structure 51) Next, a structure 51 according to a second embodiment will be described with reference to Fig. 2. Fig. 2 is a cross-sectional view schematically showing a portion of a cross section of the structure 51 according to the second embodiment. The structure 51 differs from the structure 1 in that the composite film 12 contains a plurality of zinc oxide particles 12c. The zinc oxide particles 12c are conductive.

[0042] The composite film 12 containing zinc oxide particles 12c is formed by applying a raw material solution containing cellulose nanocrystal aggregates and alkoxysilane zinc oxide particles 12c to the surface of a substrate 11, and then hydrolyzing and dehydrating and condensing the alkoxysilane in the raw material solution applied to the surface of the substrate 11. In one embodiment of the present invention, the volume-based average particle size of the zinc oxide particles 12c is 10 to 150 nm. The volume-based average particle size of the zinc oxide particles 12c is measured by a laser diffraction scattering method in accordance with JIS Z 8825. The zinc oxide particles 12c are added at a concentration of, for example, 3 to 9 wt % relative to 100 wt % of the raw material solution.

[0043] The structure 51 has a surface resistivity of 1×10 by including zinc oxide particles 12c having a volume-based average particle size of nano-order in the composite film 12. 9 ~1×10 13 Therefore, by including zinc oxide particles 12c in the composite film 12, charging of the structures 51 can be suppressed.

[0044] 3 Third embodiment (structure 61) Next, a structure 61 according to a third embodiment will be described with reference to Fig. 3. Fig. 3 is a cross-sectional view schematically showing a portion of a cross section of the structure 61 according to the third embodiment. The structure 61 differs from the structure 1 in that the composite film 12 contains a plurality of silver nanoparticles 12d.

[0045] The composite film 12 containing silver nanoparticles 12d is formed by applying a raw material solution containing cellulose nanocrystal aggregates, alkoxysilane, and silver nanoparticles 12d to the surface of the substrate 11, and then dehydrating and condensing a hydrolyzate obtained by hydrolyzing the alkoxysilane in the raw material solution applied to the surface of the substrate 11. In one embodiment of the present invention, the volume-based average particle size of the silver nanoparticles 12d is 1 to 10 nm. The volume-based average particle size of the silver nanoparticles 12d is measured by a laser diffraction scattering method in accordance with JIS Z 8825. The silver nanoparticles 12d are added at a concentration of, for example, 2 to 100 ppm (0.002 to 0.01 wt%) relative to 100 wt% of the raw material solution.

[0046] By including silver nanoparticles 12d in composite film 12, structure 61 satisfies the antibacterial test of JIS Z 2801. Therefore, by including silver nanoparticles 12d in composite film 12, it is possible to impart antibacterial properties to the surface of structure 61.

[0047] 3. Working Example The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0048] 3-1 Sample preparation Ten types of samples were prepared in the following manner.

[0049] 3-1-1 Preparation of raw material solution (raw material solution A) for composite membrane 12 A mixed solution was prepared by dissolving alkoxysilane-containing silicone in alcohol. The amount of alcohol added to this mixed solution was adjusted so that when the mixed solution was applied to a silicon substrate, the thickness of the cured film remaining on the silicon substrate after the alcohol evaporated would be 200 nm. Next, 10 wt% of powdered cellulose nanocrystal aggregates was prepared based on 100 wt% of the mixed solution. The volume-based average particle size (D50) of this cellulose nanocrystal aggregate was 2 μm. This cellulose nanocrystal aggregate was dispersed in the mixed solution to obtain a raw material solution (raw material solution A).

[0050] 3-1-2 Preparation of raw material solutions (raw material solutions B to D) for functional membrane 13 As raw material solutions for the functional film 13, the following raw material solutions B to D were prepared. A PFPE (perfluoropolyether) solution containing alkoxysilane at a concentration of 0.2 wt % was prepared as raw material solution B. A solution was prepared as raw material solution C by dissolving a hydrocarbon having alkoxysilane at a concentration of 0.5 wt % in a mixed solution of xylene and toluene in a 1:1 ratio. A solution obtained by diluting an isocyanate silane compound (Orgatix SIC330 manufactured by Matsumoto Fine Chemical Co., Ltd.) five times with ethyl acetate was prepared as raw material solution D.

[0051] 3-1-3 Preparation of Sample 1 (Example 1) A stainless steel (SUS304) plate measuring 30 mm wide, 80 mm long, and 0.15 mm thick was prepared as the substrate. This substrate was ultrasonically cleaned using isopropyl alcohol (IPA). After cleaning, raw material solution A was applied to the surface of the substrate. The substrate coated with raw material solution A was left in an environment at room temperature and 60% relative humidity for three days to allow dehydration condensation of the alkoxysilane in the coating of raw material solution A. As this dehydration condensation reaction progressed, the coating of raw material solution A became a composite film containing cellulose nanocrystal aggregates and an organic-inorganic hybrid glass covering the cellulose nanocrystal aggregates. Next, raw material solution B was applied to the surface of the composite film. The substrate coated with raw material solution B was left in an environment at room temperature and 60% relative humidity for three days to allow self-assembly of the perfluoropolyether to proceed, forming a self-assembled monolayer (functional film) of a fluorine compound on the surface of the composite film. The structure fabricated in this manner was designated Sample 1. The structure of sample 1 is a laminate comprising a substrate, a composite film containing cellulose nanocrystal aggregates provided on the surface of the substrate and organic-inorganic hybrid glass covering the cellulose nanocrystal aggregates, and a self-assembled monolayer of a fluorine compound covering the surface of the composite film.

[0052] 3-1-4 Preparation of Sample 2 (Example 2) Similar to Sample 1, a composite film containing cellulose nanocrystal aggregates and an organic-inorganic hybrid glass covering the cellulose nanocrystal aggregates was formed on the surface of a stainless steel (SUS304) substrate. The surface of this composite film was then subjected to oxygen plasma treatment in a vacuum to hydrophilize the surface so that the contact angle with water was 10° or less. Next, raw material solution C was applied to the plasma-treated surface of the composite film. The substrate coated with raw material solution C was left in an environment of room temperature and 60% relative humidity for three days to promote self-assembly of hydrocarbons, thereby forming a self-assembled monolayer of hydrocarbon compounds on the surface of the composite film. The structure of Sample 2 thus fabricated is a laminate consisting of a substrate, a composite film containing cellulose nanocrystal aggregates and an organic-inorganic hybrid glass covering the cellulose nanocrystal aggregates provided on the surface of the substrate, and a self-assembled monolayer of hydrocarbon compounds covering the surface of the composite film.

[0053] 3-1-5 Preparation of Sample 3 (Example 3) As with Sample 1, a composite film containing cellulose nanocrystal aggregates and an organic-inorganic hybrid glass covering the cellulose nanocrystal aggregates was formed on the surface of a stainless steel (SUS304) substrate. Next, raw material solution D was applied to the surface of this composite film. The substrate coated with raw material solution D was left in an environment at room temperature and 60% relative humidity for three days to promote self-organization of the silicone resin, thereby forming a thin film of silicone resin on the surface of the composite film. The structure of Sample 3 thus produced is a laminate consisting of a substrate, a composite film containing cellulose nanocrystal aggregates and an organic-inorganic hybrid glass covering the cellulose nanocrystal aggregates provided on the surface of the substrate, and a self-assembled monolayer of silicone resin covering the surface of the composite film.

[0054] 3-1-6 Preparation of Sample 4 (Example 4) Similar to Sample 1, a composite film containing cellulose nanocrystal aggregates and an organic-inorganic hybrid glass covering the cellulose nanocrystal aggregates was formed on the surface of a stainless steel (SUS304) substrate. Next, raw solution E was prepared by dissolving alkoxysilane-containing silicone in alcohol. The amount of alcohol added to raw solution E was adjusted so that when raw solution E was applied to a silicon substrate, the thickness of the cured film remaining on the silicon substrate after the alcohol evaporated was 200 nm. This raw solution E was then applied to the surface of the composite film. The substrate with raw solution E applied to the surface of the composite film was left in an environment at room temperature and 60% relative humidity for three days, allowing the alkoxysilane in the raw solution E coating to undergo dehydration condensation. As this dehydration condensation reaction progressed, the raw solution E coating became an interlayer film composed of organic-inorganic hybrid glass. Next, raw solution B was applied to the surface of this interlayer film. The substrate coated with raw material solution B was left in an environment of room temperature and 60% relative humidity for three days to allow self-assembly of the perfluoropolyether to proceed, forming a self-assembled monolayer (functional film) of a fluorine compound on the surface of the interlayer. The structure thus produced is designated Sample 4. The structure of Sample 4 is a laminate comprising a substrate, a composite film containing cellulose nanocrystal aggregates provided on the surface of the substrate and organic-inorganic hybrid glass covering the cellulose nanocrystal aggregates, an interlayer film made of organic-inorganic hybrid glass provided on the surface of the composite film, and a self-assembled monolayer of a fluorine compound covering the surface of the interlayer.

[0055] 3-1-7 Preparation of Samples 5 to 10 (Comparative Examples 1 to 6) Sample 5 was prepared by ultrasonically cleaning the surface of a stainless steel (SUS304) substrate using isopropyl alcohol (IPA).

[0056] Raw material solution E was applied to the surface of a stainless steel (SUS304) substrate that had been ultrasonically cleaned with isopropyl alcohol (IPA), and the substrate with raw material solution E applied was left in an environment of room temperature and relative humidity of 60% for three days to form a thin film of organic-inorganic hybrid glass on the surface of the substrate. The structure produced in this way is designated Sample 6. The structure of Sample 6 is a laminate consisting of a substrate and a thin film of organic-inorganic hybrid glass provided on the surface of this substrate.

[0057] Raw material solution A was applied to the surface of a stainless steel (SUS304) substrate that had been ultrasonically cleaned with isopropyl alcohol (IPA), and the substrate with raw material solution A applied was left in an environment of room temperature and 60% relative humidity for three days to form a composite film containing cellulose nanocrystal aggregates and organic-inorganic hybrid glass covering the cellulose nanocrystal aggregates on the surface of the substrate. The structure produced in this way is designated Sample 7. The structure of Sample 7 is a laminate consisting of a substrate and a thin film of organic-inorganic hybrid glass provided on the surface of the substrate.

[0058] A stainless steel (SUS304) substrate was ultrasonically cleaned with isopropyl alcohol (IPA) and then coated with raw material solution E. The substrate was then left at room temperature and a relative humidity of 60% for three days, forming a thin film of organic-inorganic hybrid glass on the substrate surface. Next, raw material solution B was applied to the surface of this organic-inorganic hybrid glass thin film. The substrate was then left at room temperature and a relative humidity of 60% for three days, allowing the perfluoropolyether to self-assemble, forming a self-assembled monolayer (functional film) of a fluorine compound on the surface of the organic-inorganic hybrid glass thin film. The structure thus fabricated is designated Sample 8. The structure of Sample 8 is a laminate consisting of a substrate, a thin film (not containing cellulose nanocrystals) containing organic-inorganic hybrid glass provided on the surface of the substrate, and a self-assembled monolayer of a fluorine compound covering the surface of this composite film.

[0059] A stainless steel (SUS304) substrate surface was ultrasonically cleaned with isopropyl alcohol (IPA) and coated with raw material solution E. The substrate was then left at room temperature and a relative humidity of 60% for three days, forming a thin film of organic-inorganic hybrid glass on the substrate surface. Next, raw material solution C was coated on the surface of this organic-inorganic hybrid glass thin film. The substrate was then left at room temperature and a relative humidity of 60% for three days, allowing hydrocarbon self-assembly to proceed, resulting in the formation of a self-assembled monolayer of hydrocarbon compounds on the surface of the organic-inorganic hybrid glass thin film. The structure thus fabricated is designated Sample 9. The structure of Sample 9 is a laminate consisting of a substrate, a thin film containing organic-inorganic hybrid glass (not containing cellulose nanocrystals) formed on the surface of the substrate, and a self-assembled monolayer of hydrocarbon compounds covering the surface of this composite film.

[0060] A stainless steel (SUS304) substrate surface was ultrasonically cleaned with isopropyl alcohol (IPA) and coated with raw material solution E. The coated substrate was then left in an environment at room temperature and 60% relative humidity for three days, forming a thin film of organic-inorganic hybrid glass on the substrate surface. Next, raw material solution D was coated on the surface of this organic-inorganic hybrid glass thin film. The substrate coated with raw material solution D was then left in an environment at room temperature and 60% relative humidity for three days, allowing the silicone resin to self-assemble, forming a thin film of silicone resin on the surface of the organic-inorganic hybrid glass thin film. The structure thus fabricated is designated Sample 10. The structure of Sample 10 is a laminate consisting of a substrate, a thin film containing organic-inorganic hybrid glass (not containing cellulose nanocrystals) formed on the surface of the substrate, and a thin film of silicone resin covering the surface of this composite film.

[0061] 3-2 Evaluation of non-adhesiveness of each sample An 18 mm wide piece of cellophane tape (product name: 405-18) manufactured by Nichiban Co., Ltd. was attached to each of Samples 1 to 10 by pressing and rubbing with a finger. The cellophane tape attached to each sample was peeled off in a 90° direction, and the strength with which the cellophane tape adhered to the sample surface was evaluated based on the following evaluation criteria. According to these evaluation criteria, a lower score indicates lower adhesiveness (i.e., higher non-adhesiveness). 1: Almost no adhesion 2: Not very sticky 3: Sticks but comes off easily 4: Sticky 5: Strong adhesion The scoring results are shown in Table 1.

[0062] The contact angle with water (pure water) was measured on the surface of each of Samples 1 to 10. The measurement was carried out using a portable contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., "PCA-11") under the following conditions. Measurement range: 0 to 180° (display resolution 0.1°) Measurement method: Contact angle measurement (droplet method) Measurement liquid: Pure water Volume: 1.5 μl Temperature: 25℃±5℃ Humidity: 45%±10% normal pressure

[0063] The above scoring results and the contact angle measurement results are summarized for each sample in Table 1 below. [Table 1]

[0064] From the above evaluation results, it was confirmed that Examples 1 to 4, in which a composite film containing cellulose nanocrystal aggregates and organic-inorganic hybrid glass is provided on the surface of the substrate 11 and a functional film containing molecules with low surface free energy (fluorine compounds, hydrocarbon compounds, or silicone resins) is provided on the surface of the composite film, were scored as 1 to 2, indicating a non-stickiness rating, and exhibited higher non-stickiness than the comparative examples, which were scored as 3 to 5.

[0065] Comparing Example 1 with Comparative Example 4, Example 2 with Comparative Example 5, and Example 3 with Comparative Example 6, it can be seen that Examples 1, 2, and 3, in which cellulose nanocrystal aggregates covered with organic-inorganic hybrid glass are provided on the surface of the substrate, have improved non-stick properties compared to Comparative Examples 4, 5, and 6, in which cellulose nanocrystal aggregates are not contained in the organic-inorganic hybrid glass film. These results confirm that providing a composite layer containing cellulose nanocrystal aggregates and organic-inorganic hybrid glass on the surface of the substrate can improve the non-stick properties of the structure. The reason why the non-stick properties of Examples 1, 2, and 3 are improved compared to Comparative Examples 4, 5, and 6 is thought to be because the cellulose nanocrystal aggregates provided on the surface of the substrate give the structure an uneven surface.

[0066] To evaluate the durability of the non-adhesive properties, the above cellophane tape was applied and peeled off 1000 times for Samples 1 and 4. After the 100th, 300th, 500th, and 1000th peeling, the strength of adhesion to the sample surface was scored based on the above evaluation criteria, and the contact angle with pure water was also measured. The scoring results and the contact angle measurement results are summarized in Table 2 below. [Table 2]

[0067] Experiments to evaluate the durability of this non-stick property confirmed that the non-stick properties hardly deteriorated even after the pressure exerted when peeling off cellophane tape was applied 1,000 times.

[0068] 4 Notes The dimensions, materials, and arrangements of each component described in the various embodiments above are not limited to those explicitly described in each embodiment, and each component can be modified to have any dimensions, materials, and arrangements that may fall within the scope of the present invention.

[0069] Components not explicitly described in this specification may be added to each of the above-described embodiments, and some of the components described in each embodiment may be omitted.

[0070] The designations "first," "second," "third," etc. in this specification are used to identify components and do not necessarily limit the number, order, or content thereof. Furthermore, numbers used to identify components are used in different contexts, and numbers used in one context do not necessarily indicate the same configuration in another context. Furthermore, this does not prevent a component identified by a certain number from also serving the function of a component identified by another number.

[0071] In this specification, when a certain component is referred to as "comprising" another component, it does not mean that other components are excluded, but that other components may be further included, unless it is inconsistent with the content of the present invention.

[0072] 5. Supplementary Notes The embodiments disclosed herein also include the following:

[0073] [Appendix 1] A substrate (11), a composite film (12) provided on the surface of the substrate, the composite film including a plurality of cellulose nanocrystal aggregates (12a) and a coating layer (12b) made of organic-inorganic hybrid glass covering the plurality of cellulose nanocrystal aggregates; a non-adhesive functional film (13) provided on the surface of the composite film; A structure comprising: [Appendix 2] The thickness of the coating layer is thinner than the average particle size of the plurality of cellulose nanocrystal aggregates. 1. The structure described in Appendix 1. [Appendix 3] The organic-inorganic hybrid glass contains siloxane. 1. The structure of claim 1 or 2. [Appendix 4] At least a portion of the cellulose nanocrystal aggregates are chemically bonded to the siloxane. The structure described in Appendix 3. [Appendix 5] The composite film further comprises conductive zinc oxide particles. 10. The construct of any one of claims 1 to 4. [Appendix 6] The composite film further comprises silver nanoparticles. 6. The construct of any one of Appendix 1 to Appendix 5. [Appendix 7] The functional film contains at least one compound selected from the group consisting of a fluorine compound, a hydrocarbon compound, and a silicone resin. 10. The construct of any one of claims 1 to 6. [Appendix 8] the functional film is a self-assembled monolayer having a water-repellent functional group at one end; 8. The construct of any one of Appendix 1 to Appendix 7. [Appendix 9] the functional film has, at the other end thereof, a functional group having excellent bonding properties with the organic-inorganic hybrid glass; 10. The structure described in Appendix 8. [Appendix 10] providing a substrate; A step of applying a raw material solution containing a plurality of cellulose nanocrystal aggregates and an alkoxysilane to the surface of the substrate, and dehydrating and condensing the alkoxysilane on the surface of the substrate to form a composite film on the surface of the substrate; forming a non-adhesive functional film on the surface of the composite film; A method for manufacturing a non-adhesive structure comprising: [Explanation of symbols]

[0074] 1, 51, 61 structure 11 Base material 12 Composite membrane 12a Cellulose nanocrystal aggregates 12b Covering layer 12c Zinc oxide particles 12d silver nanoparticles 13 Functional membranes

Claims

1. A substrate; a composite film provided on the surface of the substrate, the composite film including a plurality of cellulose nanocrystal aggregates and a coating layer made of organic-inorganic hybrid glass covering the plurality of cellulose nanocrystal aggregates; a non-adhesive functional film provided on the surface of the composite film; A structure comprising:

2. The thickness of the coating layer is thinner than the average particle size of the plurality of cellulose nanocrystal aggregates. The structure of claim 1 .

3. The organic-inorganic hybrid glass contains siloxane. The structure according to claim 1 or 2.

4. At least a portion of the plurality of cellulose nanocrystal aggregates are chemically bonded to the siloxane; The structure of claim 3.

5. The composite film further comprises conductive zinc oxide particles. The structure according to claim 1 or 2.

6. The composite film further comprises silver nanoparticles. The structure according to claim 1 or 2.

7. The functional film contains at least one compound selected from the group consisting of a fluorine compound, a hydrocarbon compound, and a silicone resin. The structure according to claim 1 or 2.

8. the functional film is a self-assembled monolayer having a water-repellent functional group at one end; The structure according to claim 1 or 2.

9. the functional film has, at the other end thereof, a functional group having excellent bonding properties with the organic-inorganic hybrid glass; The structure of claim 8.

10. providing a substrate; A step of applying a raw material solution containing a plurality of cellulose nanocrystal aggregates and an alkoxysilane to the surface of the substrate, and dehydrating and condensing the alkoxysilane on the surface of the substrate to form a composite film on the surface of the substrate; forming a non-adhesive functional film on the surface of the composite film; A method for manufacturing a non-adhesive structure comprising:

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