layers and structures

Abstract

The purpose of this invention is to suppress ice growth on a substrate. The layer of this invention forms a thin ice layer with a thickness of less than 1 mm on its surface, consisting of arranged ice nuclei.

Description

Technical Field

[0001] This invention relates to layers and structures. Background Technology

[0002] It is known that certain polymers can inhibit the growth of ice crystals in water and the formation of ice and frost on substrates. These polymers can be used as so-called ice crystal growth inhibitors or ice and frost inhibitors in heat storage systems, heat exchangers, aircraft, electrical wires, plastic greenhouses, power generation turbines, etc. Patent Document 1 describes an ice crystal growth inhibitor comprising a polymer with a carbon chain as the main chain and nitrogen-containing functional groups in the side chains. Patent Document 2 describes an ice and frost inhibitor coating comprising a zwitterionic polylysine derivative.

[0003] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2006-299108 Patent Document 2: Japanese Patent Application Publication No. 2022-187419 Summary of the Invention

[0004] The problem that the invention aims to solve In some cases, known compounds are insufficient to adequately suppress ice growth on a substrate. The purpose of this invention is to suppress ice growth on a substrate.

[0005] Technical solutions for solving the problem The present invention includes the following solutions.

[0006] [1] A layer on which a thin layer of ice less than 1 millimeter thick and composed of arranged ice nuclei is formed on its surface.

[0007] [2] As described in [1], the layer is kept for 1 minute under environmental conditions of 1,013 hPa pressure, 80 ± 5% RH humidity, and 2 ± 1 °C temperature, and then cooled to -8 ± 1 °C under the same environmental conditions to form ice nuclei with an average Freette diameter of less than 100 μm on its surface.

[0008] [3] The layer as described in [1] or [2], wherein, when cooled to -25±5°C under ambient conditions of 1,013 hPa and 20°C to 25°C, ice nuclei with an average Freret diameter of less than 100 μm are formed on its surface.

[0009] [4] The layer as described in any one of [1] to [3], wherein, after ice nuclei are formed by cooling to -25±5°C under ambient conditions of 1,013 hPa and 20°C to 25°C, and then maintained at -8±2°C for 1 hour, the average Freette diameter of the ice nuclei can be maintained below 100 μm.

[0010] [5] The layer as described in any one of [1] to [4], wherein, after being kept for 1 minute under environmental conditions of 1,013 hPa pressure, 80 ± 5% RH humidity, and 2 ± 1 °C temperature, and then cooled to -8 ± 1 °C under the same environmental conditions, a thin ice with an average film thickness of less than 1 mm is formed on its surface.

[0011] [6] The layer as described in any one of [1] to [5], wherein, after being kept for 1 minute under environmental conditions of 1,013 hPa pressure, 80 ± 5% RH humidity, and 2 ± 1 °C temperature, and then subjected to continuous repeated operation of cooling to -8 ± 1 °C and heating to 22 ± 3 °C under the same environmental conditions, a thin ice composed of arranged ice nuclei is formed on more than 95% of its surface.

[0012] [7] The layer as described in any one of [1] to [6], wherein a thin ice composed of arranged ice nuclei is formed on the surface, and after the thin ice is melted, a thin ice composed of arranged ice nuclei is formed again on the surface.

[0013] [8] The layer as described in any one of [1] to [7], wherein, after a thin ice composed of arranged ice nuclei is formed on the surface, a portion or the entire surface is immersed in water for 120 hours, and a thin ice composed of arranged ice nuclei is formed on the surface again, the shape of the thin ice formed after immersion in water is the same as the shape of the thin ice formed before immersion in water.

[0014] [9] The layer as described in any one of [1] to [8], wherein the static contact angle measured at room temperature at a time when a water droplet is 1 second behind is 30° or more and 100° or less.

[0015]

[10] The layer as described in any one of [1] to [9], wherein the surface roughness index Ra value measured in a region of 30 μm in length and 30 μm in width on the surface is 0.001 μm or more and 1.500 μm or less.

[0016]

[11] The layer as described in any one of [1] to

[10] contains a polymer having a nitrogen-containing functional group.

[0017]

[12] The layer as described in any one of [1] to

[11] contains a polymer having repeating units having a nitrogen atom equivalent of 70 g / eq or less.

[0018]

[13] The layer as described in any one of [1] to

[12] , wherein the ratio of the amount of nitrogen atoms present on the surface to the amount of carbon atoms is 0.01 or more and 0.33 or less.

[0019]

[14] The layer as described in any one of [1] to

[13] , wherein the functional group containing nitrogen atoms is a primary amino group and / or a secondary amino group, or a nitrogen-containing heterocyclic group.

[0020]

[15] The layer as described in any one of [1] to

[14] , wherein the polymer having nitrogen-containing functional groups comprises primary amino and / or secondary amino groups, or nitrogen-containing heterocyclic groups in the main chain and / or side chains.

[0021]

[16] The layer as described in any one of [1] to

[15] , wherein the polymer having a nitrogen-containing functional group is a (meth)acrylic acid (co)polymer or a (meth)acrylamide (co)polymer.

[0022]

[17] The layer as described in any one of [1] to

[16] , wherein the acid value of the polymer having a nitrogen-containing functional group is less than 100 mg KOH / g.

[0023]

[18] The layer as described in any one of [1] to

[17] is a coating film.

[0024]

[19] A membrane composed of water molecules, with a thickness of less than 20 Å. It does not exhibit the Ih phase under conditions of atmospheric pressure of 1,013 hPa and temperature of -8 ± 1 °C.

[0025]

[20] A structure having a support, and a layer as described in any one of [1] to

[18] or a membrane as described in

[19] , The aforementioned layer covers part or all of the surface of the aforementioned support.

[0026] [twenty one] The structure as described in

[20] , wherein the aforementioned layer is disposed on the outermost surface of the structure.

[0027] [twenty two] The structure as described in

[20] or

[21] further comprises a sealing layer disposed between the support and the layer. The average film thickness of the above layers is between 0.001 μm and 20 μm. The average film thickness of the aforementioned sealing layer is between 0.001 μm and 20 μm.

[0028] [twenty three] A component having a layer as described in any one of [1] to

[18] or a membrane as described in

[19] .

[0029] [twenty four] An article comprising the components described in

[23] .

[0030] Invention Effects The layers and structures of the present invention can suppress the growth of ice on a substrate. Attached Figure Description

[0031] Figure 1 middle, Figure 1 -I is the molecular structure diagram of the ice nucleus. Figure 1 -II is a conceptual diagram of a quasi-ice layer (C) formed on a polymer (B) in a solid state. Figure 1 -III is a conceptual diagram representing the layers and structures of this invention. The spheres in the diagram represent oxygen atoms. A. Support, B. Coating (layer), C. Quasi-ice layer (film), D. Thin ice composed of arranged ice nuclei. A+B is referred to as the structure.

[0032] Figure 2 This is a schematic diagram illustrating the process of placing the test piece on a cooling and heating temperature control platform.

[0033] Figure 3 This is a conceptual diagram representing the temperature control program for the test piece.

[0034] Figure 4 Images of ice formed on A. an unprocessed aluminum test piece and B. an aluminum test piece with layers of Poriment NK100PM constructed, after the temperature control program had been running for 0, 1, 2, 3, 3.5, and 4 hours.

[0035] Figure 5 This is a schematic diagram illustrating the ice formation on A. an unprocessed aluminum test piece and B. an aluminum test piece with a layer of Poriment NK100PM constructed, accompanied by a temperature control program. ○ represents water molecules present in an environment with 80% humidity. The box in B represents an ice nucleus.

[0036] Figure 6 The image shows ice formed on an aluminum test piece with layers of A. polyacrylamide and B. ammonium polyacrylate respectively.

[0037] Figure 7 These are microscopic images of ice formed on A. an unprocessed glass specimen, and ice formed on glass specimens with layers of B. polyacrylamide and C. ammonium polyacrylate, each with a thickness of 10 μm.

[0038] Figure 8 These are microscopic images of ice generated on glass slides with layers of A.Poriment NK100PM, B. poly-L-lysine, C. ε-poly-L-lysine, and D. EPOMIN SP-200, each with a thickness of 10 μm. Detailed Implementation

[0039] (First implementation method: layer) The layer of the present invention allows thin ice to form on its surface, the thickness of which is less than 1 mm and consists of arranged ice nuclei.

[0040] In water that is about to freeze when cooled to below 0°C, countless tiny water molecules, called ice nuclei, naturally crystallize. Figure 1 -I). The block formed by the repeated crystallization and random fusion of the ice nucleus is ice. In environments with approximately 80% relative humidity and a low temperature of approximately 2°C, the ice block undergoes repeated freezing and thawing, resulting in a particularly significant increase in size. This type of ice block causes deterioration or damage to supports and reduces the performance of devices utilizing heat and cold, posing a problem in industrial and medical fields.

[0041] It is known that some polymers inhibit the crystallization growth of ice nuclei in their aqueous solutions. For example, Patent Document 1 describes an aqueous solution of a polymer with a carbon chain as the main chain and nitrogen-containing functional groups in the side chains that inhibits the growth of ice nuclei in the solution. Additionally, Patent Document 2 describes an amphoteric polylysine derivative coated onto a support that delays the onset of water freezing on its coating surface. However, no substance or method has been disclosed that forms thin ice rather than solid ice, even in high-humidity and low-temperature environments where inhibiting ice formation on the support is crucial.

[0042] The layer of the present invention can suppress the formation of ice on the substrate, preferably even in high humidity and low temperature environments, suppressing the formation of ice on the support and instead forming thin ice composed of arranged ice nuclei. Furthermore, even when the thin ice is repeatedly frozen and thawed in high humidity and low temperature environments, thin ice can be formed reproducibly without the formation of ice blocks. The present invention should not be construed as being limited to any particular theory; the reason why the layer of the present invention can achieve such effects is as follows: the thickness of the layer of the present invention has the ability to form thin ice of less than 1 mm on its surface, composed of arranged ice nuclei. This thin ice, composed of arranged ice nuclei, can therefore suppress crystal growth, which is considered to suppress ice growth on the substrate.

[0043] That is, the ice nucleus ( Figure 1 The arrangement of water molecules in a solid state (I) is strictly defined; any deviation from this arrangement prevents ice nuclei from crystallizing. Therefore, the inventors conceived of the possibility that a substance in a certain solid state (I) could crystallize. Figure 1 -II, B) to create a quasi-ice layer (named QIL) Figure 1 The layers of -II and C can then utilize the arrangement of water molecules and the ice nucleus ( Figure 1 Unlike other methods, the quasi-ice layer inhibits the growth and fusion of ice nuclei attached to it, thus preventing ice formation. The inventors believe that by preventing growth through the quasi-ice layer, countless tiny ice nuclei that cannot fuse together become crowded together on the quasi-ice layer. Figure 1 –III, D), meaning that it can form “thin ice” on a macroscopic scale. Repeated and in-depth experiments revealed that the surface of the quasi-ice layer formed on the layer of this invention does not form ice blocks even in high humidity and low temperature environments; instead, thin ice forms. This thin ice is formed by countless tiny ice nuclei arranged in a uniform orientation, squeezed together. It was also confirmed that even in high humidity and low temperature environments, even with repeated freezing and thawing of the thin ice, ice blocks do not form on the structure containing the layer; instead, thin ice forms reproducibly and well, thus completing this invention.

[0044] Furthermore, according to the present invention, it is possible to know a coating (layer) of a substance that forms a thin ice solid state consisting of arranged ice nuclei instead of ice blocks, even in a high humidity and low temperature environment, as well as a support (structure) with the layer.

[0045] The ice nuclei arranged in the aforementioned thin ice are considered representative of two or more single-crystal ice crystals arranged in contact along a planar direction. Furthermore, the grain boundaries between these two or more single crystals are considered to extend in a direction perpendicular to the planar direction. This can be confirmed, for example, by observing the thin ice with an optical microscope in a direction perpendicular to the planar direction, where two or more ice nuclei are separated by boundary lines.

[0046] In a preferred embodiment, after the aforementioned layer is maintained for 1 minute under environmental conditions of 1,013 hPa, 80 ± 5% RH, and 2 ± 1 °C, and then cooled to -8 ± 1 °C under the same conditions, ice nuclei with an average Freret diameter of less than 100 μm can be formed on its surface. By forming ice nuclei with an average Freret diameter of less than 100 μm, ice growth can be suppressed.

[0047] The average Freette diameter of the ice nuclei is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 50 μm or less. For example, it can be 1 μm or more, and even more than 10 μm.

[0048] In this invention, the Ferrette diameter of the ice nucleus refers to the major axis of the rectangle circumscribed around the ice nucleus. Furthermore, in this invention, the average Ferrette diameter refers to the numerical mean of Ferrette diameters measured from 10 or more ice nuclei.

[0049] In this invention, the Ferrette diameter of the ice core can be determined by observing the thin ice from a direction perpendicular to the plane using an optical microscope.

[0050] In a preferred embodiment, when the aforementioned layer is cooled to -25±5°C under ambient conditions of 1,013 hPa and 20°C to 25°C, ice nuclei with an average Freret diameter of less than 100 μm can be formed on its surface. By forming ice nuclei with an average Freret diameter of less than 100 μm, ice growth can be suppressed.

[0051] The average Freette diameter of the ice nuclei is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 50 μm or less. For example, it can be 1 μm or more, and even more than 10 μm.

[0052] In a preferred embodiment, after the aforementioned layer is cooled to -25±5°C under an ambient pressure of 1,013 hPa and a temperature of 20°C to 25°C to form ice nuclei, and then maintained at -8±2°C for 1 hour, the average Freret diameter of the ice nuclei can be maintained below 100 μm. By forming ice nuclei with an average Freret diameter of less than 100 μm, ice growth can be suppressed.

[0053] The average Freette diameter of the ice nuclei after being kept at -8±2℃ for 1 hour is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 50 μm or less. For example, it can be 1 μm or more, and even more preferably 10 μm or more.

[0054] In a preferred embodiment, after the aforementioned layer is maintained for 1 minute under environmental conditions of 1,013 hPa pressure, 80 ± 5% RH humidity, and 2 ± 1°C temperature, and then subjected to continuous and repeated cooling to -8 ± 1°C and heating to 22 ± 3°C under these conditions, a thin layer of ice composed of arranged ice nuclei can form on more than 95% of its surface. By being able to form thin ice in such an area ratio, ice growth can be suppressed over a large area.

[0055] In the surface of the aforementioned layer, the proportion of the area of ​​the thin ice formed by the arrangement of ice nuclei is preferably 95% or more, more preferably 98% or more, even more preferably 99% or more, and less than 100%.

[0056] The presence or absence of the thin ice formed by the arrangement of ice nuclei can be confirmed by observing the surface of the aforementioned layer using an optical microscope.

[0057] In a preferred embodiment, after the aforementioned layer is maintained for 1 minute under environmental conditions of 1,013 hPa, 80 ± 5% RH, and 2 ± 1°C, and then cooled to -8 ± 1°C under the same conditions, a thin ice film with an average thickness of less than 1 mm can be formed on its surface. By forming a thin ice film with an average thickness of less than 1 mm, ice growth can be suppressed.

[0058] The average film thickness of the aforementioned thin ice is preferably 1 mm or less, more preferably 0.8 mm or less, and even more preferably 0.5 mm or less. For example, it can be 1 μm or more, and even more preferably 10 μm or more.

[0059] In this invention, the film thickness of the thin ice can be measured by observing the thin ice from a planar direction using an optical microscope. Furthermore, in this invention, the average film thickness of the thin ice refers to the value obtained by averaging the film thickness measurements taken at 10 or more locations.

[0060] In a preferred embodiment, the aforementioned layer forms a thin layer of ice on its surface composed of arranged ice nuclei. After this thin layer of ice melts, it can re-form a thin layer of ice composed of arranged ice nuclei on the surface. That is, even after the thin layer of ice melts, cooling the layer allows it to re-form a thin layer of ice. Furthermore, the aforementioned layer can further form a thin layer of ice even under repeated heating and cooling.

[0061] The number of times heating and cooling can be repeated is preferably 1 or more, more preferably 5 or more, and even more preferably 8 or more. The upper limit is, for example, according to the number of heating and cooling cycles of the aluminum fins used in the heat exchanger, such as 20,000 or less, more preferably 10,000 or less, and even more preferably 2,000 or less.

[0062] In a preferred embodiment, after a thin layer of ice composed of arranged ice nuclei is formed on the surface of the aforementioned layer, if a portion or the entire surface is immersed in water for 120 hours, and a thin layer of ice composed of arranged ice nuclei is formed again on the surface, the shape of the thin ice formed after immersion in water can be the same as the shape of the thin ice formed before immersion in water. That is, even when a thin layer of ice composed of arranged ice nuclei is formed, and the thin ice is immersed in water under conditions that promote crystal growth, the aforementioned layer can maintain the structure of the ice nuclei. Therefore, in the aforementioned layer, the crystal growth of ice can be suppressed.

[0063] Whether the shapes of the aforementioned thin ice are the same can be confirmed, for example, by the rate of change of the average Feret diameter of the ice nuclei in the thin ice, preferably 0% to 10%, more preferably 0% to 5%, and even more preferably 0% to 3%. The rate of change of the average Feret diameter of the ice nuclei in the aforementioned thin ice can be calculated, for example, as (average Feret diameter of the thin ice after immersion in water - average Feret diameter of the thin ice before immersion in water) / average Feret diameter of the thin ice before immersion in water.

[0064] Furthermore, whether the shapes of the aforementioned thin ice are the same can be confirmed by the rate of change of the average film thickness of the thin ice, which is preferably 0% to 10%, more preferably 0% to 5%, and even more preferably 0% to 3%. The rate of change of the average film thickness of the thin ice can be calculated, for example, as (average film thickness of the thin ice after immersion in water - average film thickness of the thin ice before immersion in water) / average film thickness of the thin ice before immersion in water.

[0065] In a preferred embodiment, the static contact angle measured one second after water drips onto the surface at room temperature is preferably 30° to 100°, more preferably 31° to 99°, and even more preferably 32° to 98°. With a static contact angle within this range, a quasi-ice layer forms on the surface, resulting in thin ice. As a result, ice (ice block) growth can be suppressed.

[0066] In this invention, the static contact angle can be measured according to JIS R 3257.

[0067] In a preferred embodiment, to form a uniform thin ice film, it is preferable to ensure that the pre-freezing (super)cooling water film present on the aforementioned layer is uniform. The surface roughness index Ra (arithmetic mean roughness) measured in a 30 μm long and 30 μm wide surface region of the aforementioned layer is preferably between 0.001 μm and 1.500 μm. With Ra values ​​within this range, the pre-freezing (super)cooling water film present on the surface of the aforementioned layer becomes uniform, allowing the formation of a thin ice film of uniform thickness. As a result, ice (ice block) growth can be suppressed.

[0068] The surface roughness index Ra value is preferably 0.001 μm or more and 1.500 μm or less, more preferably 0.004 μm or more and 1.400 μm or less, and even more preferably 0.007 μm or more and 1.300 μm or less.

[0069] In this invention, the surface roughness index Ra value can be determined according to ISO 25178.

[0070] In a preferred embodiment, the ratio of the amount of nitrogen atoms present on the surface of the aforementioned layer to the amount of carbon atoms can be between 0.01 and 0.33. Within this range, a quasi-ice layer can be formed on the surface, resulting in thin ice.

[0071] The above ratio is preferably 0.01 to 0.33, more preferably 0.02 to 0.30, and even more preferably 0.03 to 0.27.

[0072] The above ratios can be determined by X-ray photoelectron spectroscopy (XPS).

[0073] In a preferred embodiment, the layer of the present invention preferably contains a polymer having nitrogen-containing functional groups. By containing a polymer with nitrogen-containing functional groups, water molecules can be randomly adsorbed onto the layer surface, and these water molecules can have a crystalline arrangement different from that of a representative crystalline phase of ice (e.g., the Ih phase). As a result, it is believed that ice crystal growth is suppressed, and the overall growth of ice is also inhibited.

[0074] Examples of functional groups containing nitrogen atoms include: amino, ammonium, imino, amide bonds, and nitrogen-containing heterocyclic groups.

[0075] Examples of amino groups mentioned above include substituted or unsubstituted amino groups such as primary, secondary, and tertiary amino groups. Examples of substituents for these amino groups include: C... 1－10 Alkyl and C 1－10 Alkyl group.

[0076] As substituents for the aforementioned ammonium group, examples include: C 1－10 Alkyl and C 1－10 Alkyl groups, as the paired bases of this ammonium group, can include halogen atoms such as chlorine atoms. Specific examples of the aforementioned ammonium groups include trimethylammonium chloride, triethylammonium chloride, triethylammonium chloride, and trihydroxyethylammonium chloride.

[0077] The amide bond mentioned above is, for example, -NR. 10 The group represented by -CO-, R 10 Represents a hydrogen atom or C 1－20 Hydrocarbon group. R 10 C shown 1－20 The preferred hydrocarbon group is C.1－10 Alkyl, more preferably C 1－5 Alkyl, more preferably C 1－3 alkyl.

[0078] The aforementioned nitrogen-containing heterocyclic group can be any monocyclic or polycyclic group. Preferably, the aforementioned heterocyclic group is a 5-membered to 10-membered ring, more preferably a 5- to 9-membered ring, further preferably a 5- to 6-membered ring, and even more preferably a 5-membered ring. Examples of nitrogen-containing heterocyclic groups include: monocyclic and 5-membered nitrogen-containing heterocyclic groups such as pyrrolidinyl, pyrrolidinyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolinyl, triazolyl, and tetrazolyl; monocyclic and 6-membered nitrogen-containing heterocyclic groups such as piperidinyl, pyridinyl, morpholinyl, pyridazinyl, pyrimidinyl, and pyrazinyl; and polycyclic nitrogen-containing heterocyclic groups such as indolyl, isoyindolyl, benzimidazolyl, purine, benzotriazolyl, quinolinyl, isoquinolinyl, quinazolinyl, and quinoxalinyl.

[0079] As the nitrogen-containing heterocyclic group mentioned above, a 5-membered ring nitrogen-containing heterocyclic group is preferred, and an oxazolyl group is more preferred.

[0080] The aforementioned nitrogen-containing functional groups are preferably amino or nitrogen-containing heterocyclic groups, more preferably primary amino and / or secondary amino groups, or nitrogen-containing heterocyclic groups, and even more preferably primary amino and / or secondary amino groups.

[0081] As for the aforementioned polymers having nitrogen-containing functional groups, polymers having nitrogen-containing functional groups in the main chain and / or side chains are preferred; polymers having one or more groups selected from amino, ammonium, imino, amide bonds and nitrogen-containing heterocyclic groups in the main chain and / or side chains are more preferred; polymers having amino or nitrogen-containing heterocyclic groups in the main chain and / or side chains are even more preferred; polymers having primary amino and / or secondary amino groups or nitrogen-containing heterocyclic groups in the main chain and side chains are even more preferred; and polymers having primary amino and / or secondary amino groups in the main chain and side chains are even more preferred.

[0082] Examples of polymers with nitrogen-containing functional groups include: (meth)acrylic acid (co)polymer, (meth)acrylamide (co)polymer, polyethyleneimine, poly-L-lysine, etc.

[0083] From the viewpoints of mass production, economy, and operability, (meth)acrylic acid (co)polymers or (meth)acrylamide (co)polymers are preferred as the aforementioned polymers having nitrogen-containing functional groups. The (meth)acrylic acid (co)polymer or (meth)acrylamide (co)polymer can be understood as a (meth)acrylic acid (co)polymer or (meth)acrylamide (co)polymer having nitrogen-containing functional groups.

[0084] The aforementioned (meth)acrylic acid (co)polymer can be a (co)polymer of a monomer mixture containing (meth)acrylic acid monomers, and the aforementioned (meth)acrylamide (co)polymer can be a (co)polymer of a monomer mixture containing (meth)acrylamide monomers. Examples of monomers that can be included in such a monomer mixture include: unsaturated carboxylic acids, (meth)acrylates, hydroxyl-containing monomers, amino-containing monomers, amide-containing monomers, unsaturated carboxyl ammonium salts, unsaturated quaternary ammonium salts, vinyl ethers, vinyl esters, N-vinyl compounds, unsaturated alcohols, unsaturated amines, unsaturated sulfonic acids, (meth)acrylonitrile, etc.

[0085] Specifically, monomers that may be included in the above-mentioned monomer mixture include: unsaturated carboxylic acids such as (meth)acrylic acid; (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, and hydroxymethylcyclohexyl (meth)acrylate; hydroxyl-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; amino-containing monomers such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and butylaminoethyl (meth)acrylate; and aminoethyl (meth)acrylamide, dimethylaminomethyl (meth)acrylamide, and methylaminopropyl (meth)acrylamide. Other monomers containing amide groups, such as amines, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, methoxybutyl (meth)acrylamide, and diacetone (meth)acrylamide; unsaturated carboxyam salts such as ammonium acrylate; unsaturated quaternary ammonium salts such as 2-(acryloyloxy)ethyl ammonium chloride; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl esters such as vinyl acetate; N-vinyl compounds such as N-vinylpyrrolidone; unsaturated alcohols such as allyl alcohol and methacrylic alcohol; unsaturated amines such as allylamine; unsaturated sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid; cyano-vinyl groups such as (meth)acrylonitrile and α-chloroacrylonitrile; aromatic monomers such as styrene and vinyltoluene; monomers containing nitrogen-containing heterocyclic groups such as 2-vinyloxazoline, 4-methyl-2-vinyl-2-oxazoline, and 5-methyl-2-vinyl-2-oxazoline.

[0086] The aforementioned (meth)acrylic acid (co)polymer and (meth)acrylamide (co)polymer can be manufactured by polymerizing the above-mentioned monomer mixture. Free radical polymerization and anionic polymerization are preferred methods for such polymerization, and can be carried out by any suitable method.

[0087] The weight-average molecular weight of the above-mentioned (meth)acrylic acid (co)polymer and (meth)acrylamide (co)polymer is preferably 1,000 or more and 1,000,000 or less, more preferably 3,000 or more and 500,000 or less, and even more preferably 5,000 or more and 200,000 or less.

[0088] In this invention, the weight-average molecular weight can be determined by gel permeation chromatography and can be set as a polystyrene equivalent value.

[0089] In one embodiment, the total content of the (meth)acrylic acid (co)polymer and (meth)acrylamide (co)polymer having nitrogen-containing functional groups is preferably 80% to 100% by mass, more preferably 90% to 100% by mass, and even more preferably 95% to 100% by mass, within 100% by mass of the total polymer having nitrogen-containing functional groups.

[0090] The aforementioned polyethyleneimine is a polymer having repeating units comprising amino and alkylene groups, which can be represented, for example, by the following formula: - (R) 1 -NH-) n1 - (1) In equation (1), R 1 C represents 2－10 Alkylene n1 represents an integer greater than or equal to 2.

[0091] In equation (1), R 1 C can be preferred. 2－5 Alkylene, more preferably C 2－3 Alkylene.

[0092] The aforementioned polyethyleneimine can be linear or branched, and the branches can also combine to form a ring structure.

[0093] The aforementioned polyethyleneimine can be manufactured, for example, by ring-opening polymerization of cyclic amines such as aziridine.

[0094] The weight-average molecular weight of the aforementioned polyethyleneimine is preferably 80 or more and 300,000 or less, more preferably 90 or more and 200,000 or less, and even more preferably 100 or more and 100,000 or less.

[0095] It can be a (meth)acrylic acid (co)polymer or a (meth)acrylamide (co)polymer having the aforementioned polyethyleneimine chain. Specific examples of (meth)acrylic acid copolymers having a polyethyleneimine chain include "Poriment NK100PM", "Poriment NK-200PM", "Poriment NK-350", "Poriment NK-380", "Poriment KX-EK-100", "Poriment KX-EK-100R", "Poriment KX-EK-350", and "Poriment KX-EK-350R" manufactured by Nippon Shokubai Co., Ltd.

[0096] Examples of poly-L-lysine include α-poly-L-lysine and ε-poly-L-lysine.

[0097] The weight-average molecular weight of the above-mentioned poly-L-lysine is preferably 1,000 to 30,000, more preferably 3,000 to 20,000, and even more preferably 4,500 to 15,000.

[0098] The weight-average molecular weight of the aforementioned α-poly-L-lysine is preferably 5,000 to 30,000, more preferably 9,000 to 20,000, and even more preferably 12,000 to 15,000. Furthermore, the weight-average molecular weight of ε-poly-L-lysine is preferably 1,000 to 10,000, more preferably 3,000 to 8,000, and even more preferably 4,500 to 5,000.

[0099] The polymers containing nitrogen-containing functional groups described above preferably have repeating units with a nitrogen atom equivalent of 70 g / eq or less. This nitrogen atom equivalent is preferably 70 g / eq or less, more preferably 40 g / eq or more and 68 g / eq or less, and even more preferably 30 g / eq or more and 66 g / eq or less. This repeating unit with a nitrogen atom equivalent of 70 g / eq or less can be the smallest repeating unit containing nitrogen atoms in the aforementioned polymers containing nitrogen-containing functional groups.

[0100] The acid value of the polymer having nitrogen-containing functional groups is preferably 100 mg KOH / g or less, more preferably 50 mg KOH / g or less, even more preferably 20 mg KOH / g or less, and 0 mg KOH / g or more. Because the acid value of the polymer having nitrogen-containing functional groups is within such a range, water molecules can be randomly adsorbed onto the layer surface, and these water molecules can have a crystalline arrangement different from that of a representative ice crystalline phase (e.g., the Ih phase). As a result, ice crystal growth can be suppressed, and it can be considered that the overall growth of ice is also suppressed.

[0101] The weight-average molecular weight of the polymer having nitrogen-containing functional groups is preferably 1,000 or more and 1,000,000 or less, more preferably 3,000 or more and 500,000 or less, and even more preferably 5,000 or more and 200,000 or less.

[0102] In one embodiment, the proportion of polymers having nitrogen-containing functional groups in the aforementioned layers is preferably 80% to 100% by mass, more preferably 90% to 100% by mass, and even more preferably 95% to 100% by mass, out of a total of 100% by mass of the layers. In another embodiment, the proportion of polymers having nitrogen-containing functional groups in the aforementioned layers is preferably 30% to 95% by mass, more preferably 40% to 90% by mass, and even more preferably 50% to 85% by mass, out of a total of 100% by mass of the layers.

[0103] In addition to the polymer having nitrogen-containing functional groups, the aforementioned layer may also contain other additives. Examples of such additives include: tackifiers, leveling agents, defoamers, antistatic agents, antifogging agents, UV absorbers, free radical scavengers, pigments, dyes, and fillers. The layer may also contain compounds having polyalkylene glycol chains to adjust surface wettability, and, if necessary, crosslinking agents for fixing it to the layer and / or the polymer having nitrogen-containing functional groups. Polyethylene glycol chains and polypropylene glycol chains are preferred as polyalkylene glycol chains. Examples of compounds having polyalkylene glycol chains include compounds with hydroxyl groups at the ends of the polyalkylene glycol chains, compounds with alkoxy groups at the ends of the polyalkylene glycol chains, and compounds with glycidyl alkyl ether groups at the ends of the polyalkylene glycol chains.

[0104] Specific examples of compounds having polyalkylene glycol chains include: polyethylene glycol, polypropylene glycol, polyoxytetramethylene polyoxyethylene glycol, polyoxytetramethylene polyoxypropylene glycol, polyoxyethylene alkyl ether, polyoxyethylene branched alkyl ether, polyoxyethylene oleyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene branched alkyl ether, polyoxyethylene polyoxypropylene oleyl ether, polyoxypropylene alkyl ether, polyoxypropylene branched alkyl ether, polyoxypropylene oleyl ether, polyoxyethylene monoalkylate, polyoxyethylene monooleate, Tween 20, Tween 80, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene coconut oil fatty acid glyceride, and polyoxyethylene hydrogenated castor oil. Polyoxyethylene castor oil, polyoxyethylene sorbitol tetraoleic acid, polyethylene glycol, polypropylene glycol, polyethylene glycol, polyoxyethylene stearylamine, polyoxyethylene oleylamine, polyoxyethylene alkylpropylenediamine, polyoxyethylene fatty acid monoethanolamide, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxypropylene diglyceryl ether, polyoxypropylene sorbitol, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxybutylene pentaerythritol ether, trimethylolpropane tri(polyoxytetramethylene polyoxypropylene) ether, polyethylene glycol allyl ether, polypropylene glycol allyl ether, polyethylene glycol polypropylene glycol allyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol glycidyl lauryl ether, polyethylene glycol glycidyl methyl ether, etc. The polymers containing nitrogen-containing functional groups may also include compounds formed by combining the compounds containing polyalkylene glycol chains with the nitrogen-containing functional groups through a crosslinking agent.

[0105] The crosslinking agent can be selected from any functional group of the compound having a polyalkylene glycol chain, but isocyanate compounds are preferred when the functional group is an OH group. Specific examples include: hexamethylene diisocyanate, hexamethylene diisocyanate trimer, 1,4-cyclohexyl diisocyanate, dicyclohexylmethane 4,4'-diisocyanate, 4,4'-diisocyanate-3,3'-dimethylbiphenyl diisocyanate, and isophorone diisocyanate. These isocyanate groups can be blocked by end-capping agents such as 3,5-dimethylpyrazole, diethyl malonate, methyl ethyl ketone oxime, and ε-caprolactam.

[0106] In one embodiment, the total amount of the compound having polyalkylene glycol chains and the crosslinking agent, relative to 100% by mass of the polymer having nitrogen-containing functional groups, is preferably 0% to 99% by mass, more preferably 0% to 75% by mass, and even more preferably 0% to 50% by mass. The crosslinking agent, relative to 100% by mass of the compound having polyalkylene glycol chains, is preferably 0% to 50% by mass, more preferably 0% to 40% by mass, and even more preferably 0% to 30% by mass.

[0107] In another embodiment, the total amount of the compound having polyalkylene glycol chains and the crosslinking agent, relative to 100% by mass of the polymer having nitrogen-containing functional groups, is preferably 10% by mass or more than 99% by mass, more preferably 20% by mass or more than 75% by mass, and even more preferably 25% by mass or more than 50% by mass. The crosslinking agent, relative to 100% by mass of the compound having polyalkylene glycol chains, is preferably 1% by mass or more than 50% by mass, more preferably 3% by mass or more than 40% by mass, and even more preferably 5% by mass or more than 30% by mass.

[0108] The thickness of the above-mentioned layer is preferably 0.001 μm or more and 20 μm or less, more preferably 0.01 μm or more and 10 μm or less, and even more preferably 0.05 μm or more and 5 μm or less.

[0109] There is no particular limitation on the method for forming the above-mentioned layer. For example, the above-mentioned layer can be formed by a wet coating method or a dry coating method, and it is preferred to form it by a wet coating method. The layer formed by this wet coating method is also referred to below as a coating film.

[0110] In one embodiment, the aforementioned layer can be manufactured by applying a solution containing the polymer having nitrogen-containing functional groups and additives as needed, preferably by using the solution to form a wet coating method.

[0111] In the above solution, the content of the polymer having nitrogen-containing functional groups can be arbitrarily selected according to the coating method. From the viewpoint of uniform coating and operability, it is preferably 0.01% by mass or more than 30% by mass, more preferably 0.05% by mass or more than 20% by mass, and even more preferably 0.1% by mass or more than 10% by mass. The arrangement and density of nitrogen atoms are considered to be related to the ease of formation of the quasi-ice layer, and also to the formation of thin ice.

[0112] The above-mentioned solution, as a solvent, may contain water; lower alcohols such as ethanol, butanol, and isopropanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; diols such as methyl cellosolve, ethyl cellosolve, propylene glycol, and 1-methoxy-2-propanol; aromatic hydrocarbons such as xylene and toluene; aliphatic hydrocarbons such as n-hexane and n-heptane; and esters such as ethyl acetate and butyl acetate. Among these, water and lower alcohols and diols are preferred as solvents, with water being more preferred.

[0113] Examples of wet coating methods include dip coating, spin coating, brush coating, flow coating, spray coating, roller coating, gravure coating, and similar methods.

[0114] After obtaining a precursor film by applying a solution containing the polymer with nitrogen-containing functional groups and additives as needed, it can be dried as required. This drying process removes solvents and the like.

[0115] The drying of the aforementioned precursor layer can preferably be carried out at a temperature of 0°C to 200°C, more preferably at 5°C to 180°C, and even more preferably at 10°C to 150°C, and can preferably be carried out for a time of 1 minute to 10 hours, more preferably 2 minutes to 5 hours, and even more preferably 3 minutes to 3 hours.

[0116] Examples of dry coating methods include: vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum vapor deposition) include resistance heating, electron beam, high-frequency heating using microwaves, ion beam, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0117] (Second embodiment: membrane) The scope of the present invention also includes membranes composed of water molecules with a thickness of less than 20 Å that do not exhibit the Ih phase under conditions of atmospheric pressure of 1,013 hPa and temperature of -8 ± 1 °C.

[0118] On the surface of the aforementioned membrane, ice growth can be inhibited. Specifically, water molecules typically exist in the Ih phase under conditions of 1,013 hPa and -8 ± 1 °C. Therefore, it is believed that ice crystal growth is promoted on the surface of ice in the Ih phase. However, the membrane of the present invention does not exist in the Ih phase, and the lattice arrangement of water molecules in this membrane is considered to be different from that of water molecules in the Ih phase. Therefore, even if water molecules are adsorbed on the surface of the aforementioned membrane, these water molecules do not participate in ice crystal formation, and thus ice growth is believed to be inhibited.

[0119] The thickness of the above-mentioned membrane can be less than 20 Å, preferably more than 3 Å and less than 20 Å.

[0120] In one embodiment, the membrane can be formed on the layer by maintaining the layer under environmental conditions of 1,013 hPa pressure, 80 ± 5% RH humidity, and 2 ± 1 °C temperature for 1 minute, and then cooling it to -8 ± 1 °C under the same environmental conditions.

[0121] The present invention also includes a laminate comprising the above-described layers and a membrane disposed on the above-described layers, the membrane being a membrane composed of water molecules and having a thickness of less than 20 Å, and the membrane not exhibiting the Ih phase under conditions of atmospheric pressure of 1,103 hPa and temperature of -8 ± 1 °C.

[0122] (Third implementation: Structures, components and articles) The scope of the present invention also includes structures having a support and the aforementioned layers. In such structures, the layers cover a portion or all of the surface of the support.

[0123] This structure can be used to suppress the growth of ice on its surface.

[0124] The support that can be used in this invention can be made of, for example, glass, resin (natural or synthetic resin, such as common plastic materials), metal, ceramic, semiconductor (silicon, germanium, etc.), fiber (fabric, non-woven fabric, etc.), fur, leather, wood, pottery, stone, building components, hygiene products, or any suitable material.

[0125] In a preferred embodiment, the support may be made of a metal. Examples of suitable metals include Si, Al, Cu, Fe, Ni, or Zn, or alloys containing these. The alloy is not particularly limited; examples include Fe / Ni / Cr alloys, Al / Cu alloys, etc. In a more preferred embodiment, the metal constituting the support may include Al, Cu, Fe, or SUS.

[0126] The shape of the aforementioned support is not particularly limited and can be various shapes depending on the application. For example, in addition to simple shapes such as plates or rods, the shape of the aforementioned support can also be finned, convex or concave, or have a porous structure to increase the surface area.

[0127] The aforementioned layers have the same meaning as those in the first embodiment. These layers cover part or all of the surface of the support. Preferably, these layers are disposed on the outermost surface of the structure.

[0128] The average film thickness of the above-mentioned layer is preferably 0.001 μm or more and 20 μm or less, more preferably 0.01 μm or more and 10 μm or less, and even more preferably 0.05 μm or more and 5 μm or less.

[0129] In a preferred embodiment, the structure further includes an adhesive layer disposed between the support and the layer. This adhesive layer improves the adhesion between the support and the layer.

[0130] The adhesive layer is formed by a primer. The primer contains a coupling agent having an organic reactive group and a hydrolyzable silane group within a single molecule.

[0131] The concentration of the coupling agent relative to 100% by mass of the primer can be, for example, 0.05% by mass or more, 0.1% by mass or more, or 0.5% by mass or more. The concentration of the coupling agent can be, for example, less than 100% by mass, less than 20% by mass, less than 10% by mass, or less than 5% by mass. In one embodiment, the concentration of the coupling agent relative to 100% by mass of the primer is, for example, more than 0.05% by mass and less than 100% by mass.

[0132] The coupling agent contains an organic reactive group and a hydrolyzable silane group within a single molecule. These functional groups are respectively associated with the groups located at... Figure 1 B. as described Figure 1 The functional group reaction on the surface of the A. support is recorded, which improves the adhesion between the B. coating (layer) and the A. support.

[0133] The reactive organic group (e.g., at least one of the groups "A" in the general formula of the coupling agent described below) may be present in one molecule of the coupling agent, or there may be two or more. There is no particular limitation on the reactive organic group. Examples of reactive organic groups include at least one selected from amino, glycidyl, epoxy, vinyl, methacrylate, acrylate, styrene, phenyl, isocyanate, terminal isocyanate, and mercapto. Multiple reactive organic groups may be the same type of group or different types of groups. Reactive organic groups may be glycidyl, epoxy, isocyanate, or terminal isocyanate.

[0134] The hydrolyzable group (e.g., at least one of the groups "B" in the general formula of the coupling agent described below, which together with the adjacent Si atom constitutes a hydrolyzable silane) can be present in one molecule of the coupling agent, or there can be two or more, or even three. The hydrolyzable group is not particularly limited as long as it is hydrolyzed and forms a silanol group together with the adjacent Si atom. Examples of hydrolyzable groups include alkoxy, acetoxy, and chlorine atoms. The hydrolyzable group can be an alkoxy group. The number of carbon atoms in the alkoxy group can be 1 to 5, 1 to 3, or 1 or 2. The coupling agent can have two or more alkoxy groups with a number of carbon atoms of 1 to 5 bonded to Si. Multiple hydrolyzable groups can be the same type of group or different types of groups. The carbon chain of the alkoxy group can be linear or branched.

[0135] Examples of hydrolyzable silanes include: trimethoxysilane, triethoxysilane, tripropoxysilane, tri(2-methoxyethoxy)silane, dimethoxyalkylsilane, diethoxyalkylsilane, dipropoxyalkylsilane, and bis(2-methoxyethoxy)alkylsilane. A hydrolyzable silane can be at least one of trimethoxysilane and triethoxysilane.

[0136] Coupling agents can be represented by, for example, the following general formula: (R) A -R CP ) 4－ns -Si-R B ns (where R) A At least one of them is the above-mentioned organic reactive group, R B At least one of them is the above-mentioned hydrolyzable group, R CP Each group is an organic group that is independently either a single bond or divalent, and ns is an integer between 1 and 3.

[0137] "-Si-R B ns "Constitutes a hydrolyzable silane. In the above general formula, R other than the organic reactive group..." A For example, it could be a hydrogen atom. In the above general formula, R other than the hydrolyzable group B For example, it can be a hydrocarbon group. ns can be 2 or more, or it can be 3.

[0138] In the above general formula, R CP It can be a single bond or a divalent organic group, and can be a divalent organic group. As R CP Examples include C. 1－6 Alkylene, -(CH2) cp1 -O-(CH2) cp2 - (cp1 is an integer from 1 to 6, cp2 is an integer from 1 to 6.) or -phenylene-(CH2) cp3 - (cp3 is an integer from 0 to 6.) R CP It can be C 1－3 Alkylene, which can be C 2－3 Alkylene groups can also be -CH2CH2CH2-. These groups can be selected, for example, from fluorine atoms, C atoms, etc. 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted.

[0139] Examples of coupling agents include: vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, vinylmethyldimethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. Silane, 3-Acryloyloxypropyltrimethoxysilane, 3-Acryloyloxypropyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3 -Mercaptopropyltriethoxysilane, 3-Octaylthio-1-propyltriethoxysilane, 3-Aminopropyltriethoxysilane, 3-Aminopropyltrimethoxysilane, N-(2-Aminoethyl)-3-Aminopropyltrimethoxysilane, N-(2-Aminoethyl)-3-Aminopropylmethyldimethoxysilane, 3-(N-Phenyl)aminopropyltrimethoxysilane, 3-Triethoxysilyl-N-(1,3-Dimethyl-Butylene)propylamine, N-(ethyl The coupling agents are: (alkenylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, 3-isocyanate propyltriethoxysilane, 3-isocyanate propyltrimethoxysilane, tris(trimethoxysilylpropyl)isocyanurate, manufactured by Shin-Etsu Chemical Industry Co., Ltd. as "X-12-1195", "X-12-1293", and "X-12-1308ES". A single coupling agent can be used, or two or more can be used in combination.

[0140] The primer may also contain other additives. Examples of other additives include, for instance, tackifiers, leveling agents, defoamers, antistatic agents, anti-fogging agents, UV absorbers, free radical scavengers, pigments, dyes, and fillers. From a weather resistance perspective, the primer may contain at least one of a UV absorber and a free radical scavenger.

[0141] Examples of UV absorbers include benzophenone compounds, benzotriazole compounds, triazine compounds, free radical polymerizable compounds, and inorganic compounds. Triazine compounds can be considered UV absorbers.

[0142] Examples of benzophenone-based ultraviolet absorbers include: 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2 2'-Dihydroxy-4-methoxybenzophenone, 2,2'-Dihydroxy-4,4'-Dimethoxybenzophenone, 2,2',4,4'-Tetrahydroxybenzophenone, 4-Dodecyloxy-2-hydroxybenzophenone, 5-Benzoyl-2,4-Dihydroxybenzophenone, 2-Hydroxy-4-methoxy-2'-Carboxylbenzophenone, 2-Hydroxy-4-Stearoxybenzophenone, 4,6-Dibenzoylresorcinol.

[0143] Examples of benzotriazole-based ultraviolet absorbers include: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-octylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α'-dimethylbenzyl)phenyl]benzotriazole, 2-( 2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3”,4”,5”,6”-tetrahydrophthalimidemethyl)-5'-methylphenyl]benzotriazole, 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol].

[0144] Examples of triazine-based ultraviolet absorbers include: 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[(2-hydroxy-3-tetrateoxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

[0145] Examples of free radical polymerizable ultraviolet absorbers include: 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-methacryloyloxybenzophenone, 2-hydroxy-5-acryloyloxybenzophenone, 2-hydroxy-5-methacryloyloxybenzophenone, 2-hydroxy-4-(acryloyloxy-ethoxy)benzophenone, 2-hydroxy-4-(methacryloyloxy-ethoxy)benzophenone, 2-hydroxy-4-(methacryloyloxy-diethoxy)benzophenone, 2-hydroxy-4-(acryloyloxy-triethoxy)benzophenone, 2-(2'-hydroxy-5'-methacryloyloxyethyl-3-tert-butylphenyl)-2H-benzotriazole, and 2-(2'-hydroxy-5'-methacryloyloxypropyl-3-tert-butylphenyl)-5-chloro-2H-benzotriazole.

[0146] Examples of inorganic ultraviolet absorbers include: cerium oxide, zinc oxide, aluminum oxide, zirconium oxide, bismuth oxide, cobalt oxide, copper oxide, tin oxide, and titanium oxide.

[0147] Examples of free radical scavengers include hindered amine compounds.

[0148] Examples of hindered amine light stabilizers include: bis(2,2,6,6-tetramethyl-4-piperidinyl)succinate, bis(2,2,6,6-tetramethylpiperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynoxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynoxy]-2,2,6,6-tetramethylpiperidinyl, and bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate.

[0149] The (total) concentration of the UV absorber and / or free radical scavenger relative to 100% by mass of the primer is, for example, 1% by mass or more, 2% by mass or more, or 3% by mass or more. The (total) concentration of the UV absorber and / or free radical scavenger relative to 100% by mass of the primer is, for example, 10% by mass or less, 8% by mass or less, or 6% by mass or less. In one embodiment, the (total) concentration of the UV absorber and / or free radical scavenger relative to 100% by mass of the primer is 1% by mass or more and 10% by mass.

[0150] The primer can be diluted with an organic solvent. There are no particular limitations on the organic solvent. Examples of organic solvents include: lower alcohols such as ethanol, butanol, and isopropanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cellosolves such as methyl cellosolve and ethyl cellosolve; aromatic hydrocarbons such as xylene and toluene; aliphatic hydrocarbons such as n-hexane and n-heptane; and esters such as ethyl acetate and butyl acetate.

[0151] The aforementioned sealing layer may contain a compound comprising portions that have affinity for the aforementioned support and portions that have affinity for the aforementioned layer.

[0152] The average film thickness of the aforementioned sealing layer is preferably 0.001 μm to 20 μm, more preferably 0.01 μm to 15 μm, and even more preferably 0.05 μm to 10 μm.

[0153] The structure described above can be manufactured by forming the layer on the support, preferably by applying a solution containing a polymer having nitrogen-containing functional groups and additives as needed onto the support. The polymer, additives, solution, and method of applying the solution described above can be the same as the compounds and methods described in the first embodiment.

[0154] When the aforementioned structure has the aforementioned sealing layer, the structure can be manufactured by forming the sealing layer on the upper part of the aforementioned support and forming the aforementioned layer on the sealing layer. In this manner, the sealing layer can be formed by a coating method such as wet coating. Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roller coating, and gravure coating. The primer can be applied by spin coating.

[0155] The scope of this invention also includes components or materials having the aforementioned layer. Examples of components or materials having this layer include: heat transfer tubes, fins, valves, external fittings, covering materials, and housings.

[0156] The scope of this invention also includes articles comprising the aforementioned components or materials. Examples of such articles include: thermal storage systems, heat exchangers, aircraft, ships, vehicles, power lines, signal lights, signs, billboards, residential roofs, solar panels, plastic greenhouses, and power generation turbines.

[0157] The layers, films, structures, components, and articles of the present invention have been described in detail above. However, the layers, films, structures, components, and articles of the present invention, as well as their manufacturing methods, are not limited to the embodiments illustrated above.

[0158] According to the present invention, layers, films, structures, components, and articles capable of inhibiting ice growth can be provided. These layers, films, structures, components, and articles are preferably applicable to heat storage systems, heat exchangers, aircraft, ships, vehicles, power lines, signal lights, signs, billboards, residential roofs, solar panels, plastic greenhouses, power generation turbines, etc.

[0159] Example The invention is illustrated in more detail by way of the following embodiments, but the invention is not limited to these embodiments.

[0160] <Water contact angle (static contact angle)> The water contact angle (static contact angle) was measured using a Drop Master 701 contact angle meter manufactured by Kyowa Interface Science Co., Ltd. Specifically, 5 points were measured on one test piece using a 2 μL water droplet, and the average value was taken.

[0161] <Surface roughness (arithmetic mean roughness Ra)> Surface roughness (arithmetic mean roughness Ra) was measured using a Keyence VK-9710 laser microscope. Specifically, Ra was measured in a 30 μm square area for image data obtained at 150x objective lens. Six points were measured, and the average value was taken.

[0162] <The ratio of nitrogen atoms to carbon atoms (N / C) present on the coating surface> The ratio of nitrogen atoms to carbon atoms present on the coating surface was determined by X-ray photoelectron spectroscopy (XPS). The peak areas of the N1s and C1s orbitals were observed and calculated using a ULVAC-Phi PHI5000 VersaProbell photoelectron spectrometer under the following conditions.

[0163] X-ray source: Monochromatic AIKα line (25W) Photoelectron detection area: 1,000 μm × 300 μm Photoelectron detection angle: 45 degrees Energy: 23.5eV [Example 1] To conduct experiments using aluminum as a support, A1050 aluminum plates (0.1 mm thick) were cut with a cutting machine to obtain aluminum sheets measuring 10 × 30 × 0.1 mm in thickness.

[0164] The aluminum sheet was placed in a 50ml centrifuge tube with acetone and ultrasonically cleaned for 30 minutes to remove surface contaminants. The aluminum sheet was then removed from the centrifuge tube and placed under a BIOFORCE NANOSCIENCES Ozonecleaner PC440 for 1 minute of UV irradiation to further remove surface contaminants and simultaneously activate the negatively charged ions on the aluminum surface. On this activated aluminum sheet, an OSG System Products OSP-100 manual bar coater was used to coat a 100μm wet film of a 10wt% aqueous solution of Poriment NK100PM (Nippon Shokubai Co., Ltd.) diluted with distilled water to a 1 / 5 concentration. The aluminum sheet was then heated at 150°C for 3 minutes using a Yamato Scientific Co., Ltd. PRICE NK100PM layer to obtain an aluminum test piece with a 10μm thick Poriment NK100PM layer. The surface of the test piece has a water contact angle of 96°, a surface roughness Ra of 0.016 μm, and an N / C ratio of 0.03.

[0165] [Example 2] A 15mm diameter circular microscope coverslip (manufactured by Matsunami Glass Industry Co., Ltd.) was placed on an Ozone cleaner PC440 (manufactured by Bioforcenanosciences Co., Ltd.) and irradiated with UV light for 1 minute to remove surface contaminants. On this glass, a 100μm wet film was prepared using a manual rod coater OSP-100 (manufactured by OSG System Products Co., Ltd.) with a pre-diluted Poriment NK100PM (manufactured by Nippon Shokubai Co., Ltd.) solution of water to a 10wt% concentration. The film was then heated at 150°C for 3 minutes using a Yamato Scientific Co., Ltd. exemplified by a Poriment NK100PM layer with a thickness of 10μm. The test piece exhibited a water contact angle of 92°, a surface roughness Ra of 0.017μm, and an N / C ratio of 0.03.

[0166] [Example 3] Except for replacing "Poriment NK100PM" with "poly-L-lysine hydrochloride" manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd., the same procedures as in Example 2 were performed to obtain a glass test piece with a poly-L-lysine hydrochloride layer having a thickness of 10 μm. The water contact angle of the surface of this test piece was 64°, the surface roughness Ra was 1.159 μm, and the N / C ratio was 0.22.

[0167] [Example 4] Except for replacing "Poriment NK100PM" with "ε-poly-L-lysine 25% solution" manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd., the same operation as in Example 2 was performed to obtain a glass test piece with an ε-poly-L-lysine layer having a thickness of 10 μm. The water contact angle of the surface of this test piece was 33°, the surface roughness Ra was 0.337 μm, and the N / C ratio was 0.22.

[0168] [Example 5] Except for changing "Poriment NK100PM" to "EPOMIN SP-200" manufactured by Nippon Shokubai Co., Ltd., the same operation as in Example 2 was performed to obtain a glass test piece with a layer of EPOMIN SP-200 with a thickness of 10 μm. The water contact angle of the surface of this test piece was 34°, the surface roughness Ra was 0.012 μm, and the N / C ratio was 0.25.

[0169] [Comparative Example 1] A1050 aluminum plate (0.1mm thick) was cut with a cutting machine to obtain aluminum sheets measuring 10×30×0.1mm thick. The aluminum sheets were then placed in 50ml centrifuge tubes with acetone and ultrasonically cleaned for 30 minutes to remove surface stains, resulting in pure aluminum test pieces.

[0170] [Comparative Example 2] A1050 aluminum plate (0.1mm thick) was cut using a cutting machine to obtain aluminum sheets measuring 10×30×0.1mm thick. The aluminum sheets were placed in a 50ml centrifuge tube with acetone and then ultrasonically cleaned for 30 minutes to remove surface contaminants. The aluminum sheets were then removed from the centrifuge tube and placed in a Bioforce NANOSCIENCES Ozone cleaner PC440 for 1 minute of UV irradiation to further remove surface contaminants and simultaneously activate the negatively charged ions on the aluminum surface. On the activated aluminum sheets, an OSG System Products OSP-25 manual rod coater was used to apply a 40.0wt% aqueous solution of SIGMA-ALDRICH polyacrylamide (50wt% active ingredient, molecular weight 10,000) diluted with water to create a wet film thickness of 25μm. The aluminum sheet was heated at 130°C for 3 minutes using a Yamato Scientific Co., Ltd. DX302 high-temperature dryer to obtain an aluminum test piece with a 10 μm thick polyacrylamide layer. The surface of the test piece had a water contact angle of 17°, a surface roughness Ra of 0.018 μm, and an N / C ratio of 0.22.

[0171] [Comparative Example 3] Except for replacing the "polyacrylamide aqueous solution" with "ammonium polyacrylate solution 70-110" (42 wt% active ingredient, molecular weight 10,000) manufactured by Fujifilm and Koujun Pharmaceutical Co., Ltd., the same operation as in Comparative Example 2 was performed to obtain an aluminum test piece with an ammonium polyacrylate layer having a thickness of 10 μm. The water contact angle of the surface of this test piece was 25°, the surface roughness Ra was 0.032 μm, and the N / C ratio was 0.04.

[0172] [Comparative Example 4] A 15mm diameter circular microscope coverslip (manufactured by Matsunami Glass Industry Co., Ltd.) was placed under UV light for 1 minute using an Ozone cleaner PC440 (manufactured by Bioforcenanosciences Co., Ltd.) to remove surface contaminants. On this glass, a 25μm wet film was prepared using a manual rod coater OSP-25 (manufactured by OSG System Products Co., Ltd.) with a pre-diluted 40.0wt% solution of polyacrylamide aqueous solution (50wt% active ingredient, molecular weight 10,000) (manufactured by SIGMA-ALDRICH Co., Ltd.). The film was then heated at 130°C for 3 minutes using a Yamato Scientific Co., Ltd. DX302 high-temperature dryer to obtain a glass test piece with a 10μm thick polyacrylamide layer. The surface of this test piece had a water contact angle of 16°, a surface roughness Ra of 0.019μm, and an N / C ratio of 0.24.

[0173] [Comparative Example 5] Except for replacing the "polyacrylamide aqueous solution" with "ammonium polyacrylate solution 70-110" (42 wt% active ingredient, molecular weight 10,000) manufactured by Fujifilm and Koujun Pharmaceutical Co., Ltd., the same operation as in Comparative Example 4 was performed to obtain a glass test piece with a polyacrylate layer having a thickness of 10 μm. The water contact angle of the surface of this test piece was 26°, the surface roughness Ra was 0.035 μm, and the N / C ratio was 0.04.

[0174] Ice crystal observation like Figure 2As shown, two test pieces were attached to the upper surface of the Peltier temperature control section (40×40mm) inside the "Type 10030 Cooling and Heating Temperature Control Platform" manufactured by Japan High-Tech Co., Ltd., using "Temperature Conductivity Double-Sided Silicone Tape TC-10SAS" manufactured by Shin-Etsu Chemical Industry Co., Ltd. This allowed the temperature of each test piece to freely vary between -40°C and room temperature with an accuracy of 0.1°C / minute. The cooling and heating temperature control platform was then placed in a "Type EMU-0541 Low Temperature Chamber" manufactured by FUKUSHIMAGALILEI CO. LTD., with both test pieces positioned perpendicular to the ground. After powering on the chamber for approximately one hour, the temperature was set to 2.0±1.0°C. Next, a water tank of approximately 1 liter with a small mist-generating device was placed inside the chamber. By activating the device, mist was generated inside the chamber. This allowed the humidity inside the chamber to reach 80±5% after approximately two hours. By repeatedly starting and stopping the fog-generating device, the humidity was maintained throughout the ice crystal observation experiment. This created an environment of 2°C and 80% humidity within the low-temperature constant-temperature chamber.

[0175] Temperature Variable Program Will Figure 3 The temperature program shown applies to the "Type 10030 Cooling and Heating Temperature Control Table" manufactured by Japan High-Tech Co., Ltd., thereby varying the temperature of the test piece attached to the Peltier temperature control section between -8°C and 22°C. The smallest unit of this variable temperature program can be expressed by the following formula.

[0176] [22℃ (10 seconds) → Cool (1 minute) → -8℃ (27 minutes 50 seconds) → Heat (1 minute) →] The procedure was repeated eight times consecutively, for a total of 240 minutes (4 hours) of experimentation. The formation and melting of ice on the surface of the test piece were observed. The observations were conducted using an Apple iPad mini. The camera function of the iPad mini was used to capture changes on the test piece, and the resulting animation files were analyzed to understand the changes in the test piece under varying temperatures. Furthermore, the camera position of the iPad mini was adjusted to capture images simultaneously with a clock placed on the right side of the test piece. Figure 2 When the temperature variable program is started, the clock is set to 00:00 to enable its operation, thus clarifying the correspondence between the changes in ice on the test piece and the temperature variable program.

[0177] Changes in ice over time Figure 4The images are screenshots taken from the animation, showing the water freezing on the surface of the test piece at time points of approximately 0, 1, 2, 3, 3.5, and 4 hours after the above-mentioned temperature-variable program was activated a total of 8 times, arranged from left to right. A is the test piece of Comparative Example 1, and B is the test piece of Example 1. Both were placed vertically relative to the ground in an environment with a temperature of 2°C and humidity of 80%. Figure 2 As the temperature was cooled to -8°C, condensation immediately formed on the surface of A, and the condensed water transformed into ice with rounded, bulging, curved, convex surfaces. This ice continued to grow by absorbing surrounding water during the 27 minutes and 50 seconds it remained at -8°C, melting into water droplets upon heating to 22°C. These droplets then remained in place instead of flowing off the test piece, and upon cooling again to -8°C, transformed into ice blocks with even larger rounded, convex surfaces. This ice block growth continued with each increase in the number of temperature-variable programs. On the other hand, B did not form ice with rounded, convex surfaces, but instead formed a thin film of ice. This ice flowed off the coating as it melted. With each cooling to -8°C using the temperature-variable program, regardless of the number of times, a thin film of ice composed of arranged ice nuclei was reproducibly formed.

[0178] Figure 5 The diagram schematically illustrates the ice formed on test pieces during the implementation of a variable temperature program. A is a test piece from Comparative Example 1, and B is a test piece from Example 1. Both were placed in an environment with a temperature of 2°C and humidity of 80%. Ice with a curved, convex surface formed on the surface of A, and its size increased with each additional application of the variable temperature program. The right end of A shows the ice formed on the surface after approximately 240 minutes of repeated cooling to -8°C eight times. On the other hand, ice nuclei that had ceased crystal growth were arranged on the surface of B. This appeared macroscopically as thin ice less than 1 mm thick. This thin ice melted upon heating to 22°C, turning into water droplets that flowed down the surface of the test piece. The thin ice composed of the arranged ice nuclei was reproducibly formed with good precision during each repeated cooling to -8°C.

[0179] Figure 6 Images showing ice formation on various surfaces during the execution of a variable temperature program. A is the test piece from Comparative Example 2, and B is the test piece from Comparative Example 3. The variable temperature program was executed with a cooling and heating control table at 2°C and 80% humidity. Figure 6 As shown, the coatings of either A or B produce ice crystals with curved, convex surfaces, the size of which increases with the number of temperature-variable programs. Unlike the test piece in Comparative Example 1, the increase in ice size occurs at the bottom of the test piece, but the mechanism can be used... Figure 5 illustrate.

[0180] Figure 7These are microscopic images of ice formed on each test slide. A is a circular microscope coverslip (15 mm in diameter) manufactured by Matsunami Glass Industry Co., Ltd., B is the test slide of Comparative Example 4, and C is the test slide of Comparative Example 5. An Olympus "Biomicroscope BX53" was used, fitted with a "Type 10030 cooling and heating stage" manufactured by Japan High-Tech Co., Ltd. A 1 μL droplet of water was placed on each test slide, and its freezing process was observed under the microscope.

[0181] When the cooling rate was set to -30°C / min to lower the temperature of the stage, the water droplets on any of the glass pieces froze at approximately -25°C after being supercooled. At this freezing temperature, no arranged ice nuclei were observed in any of the glass pieces A through C. Furthermore, no arranged ice nuclei were observed when their temperature was lowered to -8°C. Ice with curved, convex surfaces formed in A; due to its thickness, it blocked light from the microscope light source, so a portion of the microscope image appeared black. Ice with such convex surfaces did not form in B and C, but no microscope images showing the arrangement of ice nuclei were obtained.

[0182] Figure 8 Is to conduct with Figure 7 Microscopic images of ice generated on each test piece were obtained using the same procedure. A is the test piece of Example 2, B is the test piece of Example 3, C is the test piece of Example 4, and D is the test piece of Example 5. When the cooling temperature of the cooling and heating stage was set to -30°C / minute, the water droplets on the coatings located at A to D all froze at around -25°C after being supercooled, turning into ice. Figure 8 The microscopic images of ice particles A through D shown were observed at the instant of freezing. Even when the temperature of the temperature control stage was raised to -8°C, these images remained unchanged. Furthermore, no changes were observed after maintaining the temperature at -8°C for one hour. The microscopic images of A through D resemble a pile of bricks, or densely packed plant cells. Sometimes they exhibit patterns similar to fern leaves. These unique patterns are observed because the individual ice nuclei are arranged in a uniform and regular pattern on the coating, resulting in a difference in refractive index between the basal and prism surfaces, which is observed as a boundary line. Figure 8 This indicates that the ice formed on points A through D consists of countless ice nuclei arranged in a dense, seamless manner. Each ice nucleus is originally hexagonal, but the quasi-ice layer cannot uniformly prevent the growth of the six prism facets, thus resulting in a skewed shape. The results show that... Figure 4 B and Figure 5 The thin ice shown in B is composed of countless ice nuclei arranged in this way.

[0183] Industrial availability According to the present invention, layers, films, structures, components, and articles capable of inhibiting ice growth can be provided. Such layers, films, structures, components, and articles are preferably applicable to heat storage systems, heat exchangers, aircraft, ships, vehicles, power lines, signal lights, signs, billboards, residential roofs, solar panels, plastic greenhouses, power generation turbines, etc.

Claims

1. A layer, characterized in that: Thin ice, less than 1 mm thick and composed of arranged ice nuclei, forms on the surface of this layer.

2. The layer as described in claim 1, characterized in that: After being kept for 1 minute under environmental conditions of 1,013 hPa, 80 ± 5% RH, and 2 ± 1 °C, and then cooled to -8 ± 1 °C under the same conditions, ice nuclei with an average Freret diameter of less than 100 μm were formed on its surface.

3. The layer as described in claim 1 or 2, characterized in that: When cooled to -25±5℃ under ambient conditions of 1,013 hPa and 20℃ to 25℃, ice nuclei with an average Freret diameter of less than 100 μm are formed on its surface.

4. The layer according to any one of claims 1 to 3, characterized in that: When ice nuclei are formed by cooling to -25±5°C under an ambient pressure of 1,013 hPa and a temperature of 20°C to 25°C, and then maintaining the temperature at -8±2°C for 1 hour, the average Feret diameter of the ice nuclei can be maintained below 100 μm.

5. The layer according to any one of claims 1 to 4, characterized in that: After being kept in an environment with an atmospheric pressure of 1,013 hPa, a humidity of 80±5% RH, and a temperature of 2±1℃ for 1 minute, and then cooled to -8±1℃ under the same conditions, a thin ice film with an average thickness of less than 1 mm is formed on its surface.

6. The layer according to any one of claims 1 to 5, characterized in that: After being kept in an environment with an atmospheric pressure of 1,013 hPa, a humidity of 80±5% RH, and a temperature of 2±1℃ for 1 minute, and then subjected to continuous repeated operations of cooling to -8±1℃ and heating to 22±3℃ under the same conditions, a thin layer of ice composed of arranged ice nuclei forms on more than 95% of its surface.

7. The layer according to any one of claims 1 to 6, characterized in that: A thin layer of ice, consisting of arranged ice nuclei, forms on the surface. After this thin layer of ice melts, another thin layer of ice, consisting of arranged ice nuclei, forms on the surface.

8. The layer as described in any one of claims 1 to 7, characterized in that: If, after a thin layer of ice consisting of arranged ice nuclei forms on a surface, a portion or the entire surface is immersed in water for 120 hours, and a thin layer of ice consisting of arranged ice nuclei forms again on the surface, the shape of the thin layer of ice formed after immersion in water is the same as the shape of the thin layer of ice formed before immersion in water.

9. The layer as described in any one of claims 1 to 8, characterized in that: On the surface, the static contact angle measured 1 second after a water droplet falls is between 30° and 100°.

10. The layer according to any one of claims 1 to 9, characterized in that: On the surface, the surface roughness index Ra value measured in a region with a length of 30 μm and a width of 30 μm is above 0.001 μm and below 1.500 μm.

11. The layer according to any one of claims 1 to 10, characterized in that: Polymers containing functional groups with nitrogen atoms.

12. The layer according to any one of claims 1 to 11, characterized in that: Polymers containing repeating units with a nitrogen atom equivalent of less than 70 g / eq.

13. The layer according to any one of claims 1 to 12, characterized in that: The ratio of the amount of nitrogen atoms present on the surface to the amount of carbon atoms is between 0.01 and 0.

33.

14. The layer according to any one of claims 1 to 13, characterized in that: The nitrogen-containing functional group is a primary amino group and / or a secondary amino group, or a nitrogen-containing heterocyclic group.

15. The layer according to any one of claims 1 to 14, characterized in that: Polymers having the nitrogen-containing functional groups contain primary and / or secondary amino groups, or nitrogen-containing heterocyclic groups, in the main chain and / or side chains.

16. The layer according to any one of claims 1 to 15, characterized in that: The polymer having nitrogen-containing functional groups is a (meth)acrylic acid (co)polymer or a (meth)acrylamide (co)polymer.

17. The layer according to any one of claims 1 to 16, characterized in that: The polymer having a nitrogen-containing functional group has an acid value of less than 100 mg KOH / g.

18. The layer according to any one of claims 1 to 17, characterized in that: It is a coating.

19. A membrane composed of water molecules, characterized in that: Thickness below 20 Å It does not exhibit the Ih phase under conditions of atmospheric pressure of 1,013 hPa and temperature of -8 ± 1 °C.

20. A structure, characterized in that: It has a support and a layer as described in any one of claims 1 to 18. The layer covers part or all of the surface of the support.

21. The structure as described in claim 20, characterized in that: The layer is disposed on the outermost surface of the structure.

22. The structure as described in claim 20 or 21, characterized in that: It also has a sealing layer disposed between the support and the layer. The average film thickness of the layer is between 0.001 μm and 20 μm. The average thickness of the sealing layer is between 0.001 μm and 20 μm.

23. A component having a layer as described in any one of claims 1 to 18.

24. An article comprising the component of claim 23.

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