Layer and structure

Abstract

The purpose of the present disclosure is to suppress the growth of ice on a substrate.　The layer according to the present disclosure is no thicker than 1 millimeter and causes thin ice made from arrays of ice nuclei to form on the surface of the layer.

Description

Layers and Structures

[0001] The present disclosure relates to layers and structures.

[0002] It is known that certain polymers can suppress 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 thermal storage systems, heat exchangers, aircraft, electric wires, greenhouses, power generation turbines, etc. Patent Document 1 describes an ice crystal growth inhibitor containing a polymer having a carbon chain as the main chain and a nitrogen atom-containing functional group in the side chain. Furthermore, Patent Document 2 describes an ice and frost suppression coating containing an amphoteric polylysine derivative.

[0003] JP 2006-299108 A JP 2022-187419 A

[0004] Conventionally known compounds have not always been able to sufficiently suppress the growth of ice on a substrate. An object of the present disclosure is to suppress the growth of ice on a substrate.

[0005] The present disclosure includes the following aspects. [1] A layer that forms thin ice having a thickness of 1 millimeter or less and composed of aligned ice nuclei on its surface. [2] The layer according to [1], which, when held for 1 minute under environmental conditions of an atmospheric pressure of 1,013 hPa, a humidity of 80±5% RH, and a temperature of 2±1°C, and then cooled to -8±1°C under the same environmental conditions, forms ice nuclei having an average Feret diameter of 100 μm or less on its surface. [3] The layer according to [1] or [2], which, when cooled to -25±5°C under environmental conditions of an atmospheric pressure of 1,013 hPa and a temperature of 20°C to 25°C, forms ice nuclei having an average Feret diameter of 100 μm or less on its surface. [4] The layer according to any one of [1] to [3], which can maintain the average Feret's diameter of the ice nuclei at 100 μm or less when cooled to −25±5° C. under environmental conditions of an atmospheric pressure of 1,013 hPa and a temperature of 20 to 25° C. to form ice nuclei, and then further maintained at −8±2° C. for one hour. [5] The layer according to any one of [1] to [4], which can form thin ice with an average film thickness of 1 mm or less on its surface when maintained for one minute under environmental conditions of an atmospheric pressure of 1,013 hPa, a humidity of 80±5% RH, and a temperature of 2±1° C., and then cooled to −8±1° C. under the same environmental conditions. [6] The layer according to any one of [1] to [5], which, when kept for 1 minute under environmental conditions of an atmospheric pressure of 1,013 hPa, a humidity of 80±5% RH, and a temperature of 2±1°C, and then continuously cooled to -8±1°C and heated to 22±3°C under the same environmental conditions, forms thin ice composed of aligned ice nuclei over 95% or more of its surface. [7] The layer according to any one of [1] to [6], which forms thin ice composed of aligned ice nuclei on its surface, melts the thin ice, and then forms thin ice composed of aligned ice nuclei again on its surface. [8] The layer according to any one of [1] to [7], which, after forming thin ice composed of aligned ice nuclei on its surface, immerses a part or the entire surface in water for 120 hours, and then forms thin ice composed of aligned ice nuclei again on its surface, and 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. [9] The layer according to any one of [1] to [8], wherein the static contact angle of water measured at room temperature one second after impact on the surface is 30° or more and 100° or less.

[10] The layer according to any one of [1] to [9], wherein the surface roughness index Ra measured in an area of ​​30 μm lengthwise and 30 μm widthwise is 0.001 μm or more and 1.500 μm or less.

[11] The layer according to any one of [1] to

[10] , comprising a polymer having a functional group containing a nitrogen atom.

[12] The layer according to any one of [1] to

[11] , comprising a polymer having a repeating unit with a nitrogen atom equivalent of 70 g / eq or less.

[13] The layer according to any one of [1] to

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

[14] The layer according to any one of [1] to

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

[15] The layer according to any one of [1] to

[14] , wherein the polymer having a functional group containing a nitrogen atom contains a primary and / or secondary amino group or a nitrogen-containing heterocyclic group in the main chain and / or side chain.

[16] The layer according to any one of [1] to

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

[17] The layer according to any one of [1] to

[16] , wherein the acid value of the polymer having a functional group containing a nitrogen atom is 100 mgKOH / g or less.

[18] The layer according to any one of [1] to

[17] , wherein the layer is a coating film.

[19] A film composed of water molecules, having a thickness of 20 Å or less, and not exhibiting an Ih phase under conditions of an atmospheric pressure of 1,013 hPa and a temperature of -8±1°C.

[20] A structure comprising a support and the layer according to any one of [1] to

[18] or the film according to

[19] , wherein the layer or film covers a part or all of the surface of the support.

[21] The structure according to

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

[22] The structure according to

[20] or

[21] , further comprising an adhesive layer disposed between the support and the layer, wherein the layer has an average film thickness of 0.001 μm or more and 20 μm or less, and the adhesive layer has an average film thickness of 0.001 μm or more and 20 μm or less.

[23] A member comprising the layer according to any one of [1] to

[18] or the film according to

[19] .

[24] An article comprising the member according to

[23] .

[0006] The layers and structures of the present disclosure can inhibit ice growth on a substrate.

[0007] Figure 1-I is a diagram of the molecular structure of ice nuclei. Figure 1-II is a conceptual diagram of a pseudo-ice layer (C) formed on a solid-state polymer (B). Figure 1-III is a conceptual diagram showing the layers and structures of the present invention. The spheres in the diagram represent oxygen atoms. A. Support, B. Coating film (layer), C. Pseudo-ice layer (film), D. Thin ice consisting of arranged ice nuclei. A + B is referred to as the structure. Figure 2 is a schematic diagram showing how to set a test specimen on a cooling and heating stage. Figure 3 is a conceptual diagram showing the temperature control program for the test specimen. Figure 4 is an image of ice formed on A. an unprocessed aluminum test specimen and B. an aluminum test specimen with a layer of Polyment NK100PM at 0, 1, 2, 3, 3.5, and 4 hours after the temperature control program was activated. Figure 5 is an image of ice formed on A. an unprocessed aluminum test specimen and B. an aluminum test specimen with a layer of Polyment NK100PM, following the temperature control program. This is a schematic diagram showing ice formation on an aluminum test piece constructed with a layer of Polyment NK100PM. The circles represent water molecules present in an 80% humidity environment. The squares in B represent ice nuclei. Figure 6 shows images of ice formation on aluminum test pieces constructed with layers of A. polyacrylamide and B. ammonium polyacrylate. Figure 7 shows microscopic images of ice formation on A. an untreated glass test piece and on glass test pieces constructed with 10 μm-thick layers of B. polyacrylamide and C. ammonium polyacrylate. Figure 8 shows microscopic images of ice formation on glass test pieces constructed with 10 μm-thick layers of A. Polyment NK100PM, B. poly-L-lysine, C. ε-poly-L-lysine, and D. Epomin SP-200.

[0008] First Embodiment: Layer The layer of the present disclosure allows thin ice to form on its surface, the thin ice being 1 millimeter or less in thickness and consisting of aligned ice nuclei.

[0009] When water is cooled to below 0°C and on the verge of freezing, countless tiny crystals of water molecules called ice nuclei spontaneously form (Figure 1-I). These ice nuclei repeatedly grow and randomly fuse to form ice blocks. Repeated freezing and thawing of ice blocks in a high relative humidity of approximately 80% and a low temperature of approximately 2°C increases their size. The ice blocks formed in this way cause deterioration and damage to support materials, reducing the performance of various devices that utilize cold energy, which has been a problem in the industrial and medical fields.

[0010] It is known that certain polymers inhibit the crystal growth of ice nuclei in their aqueous solutions. For example, Patent Document 1 describes that an aqueous solution of a polymer having a carbon chain as its main chain and a nitrogen-containing functional group in its side chain inhibits the growth of ice nuclei in the solution. Patent Document 2 also describes that an amphoteric polylysine derivative applied to a support delays the time until water begins to freeze on the applied surface. However, no substance or method has been clarified that can form thin ice instead of ice blocks even in high-humidity, low-temperature environments, which is important for inhibiting ice block formation on a support.

[0011] The layer of the present disclosure can suppress the formation of ice blocks on a substrate, preferably even in a high-humidity, low-temperature environment, by suppressing the formation of ice blocks on a support and instead allowing thin ice consisting of aligned ice nuclei to form. Furthermore, even when the thin ice is repeatedly frozen and thawed in a high-humidity, low-temperature environment, thin ice can be reproducibly formed instead of ice blocks. While the present disclosure should not be interpreted as being limited to a particular theory, the reason why the layer of the present disclosure can achieve such an effect is believed to be as follows: That is, the layer of the present disclosure has the ability to form thin ice on its surface that is 1 millimeter or less thick and consists of aligned ice nuclei. Because the thin ice is composed of aligned ice nuclei, crystal growth can be suppressed, which is thought to result in the suppression of ice growth on the substrate.

[0012] In other words, the arrangement of water molecules that make up ice nuclei (Figure 1-I) is strictly determined, and if this arrangement is misaligned, the ice nuclei cannot grow into crystals. Based on this, the inventors came up with the idea that if they create a pseudo-ice layer (named Quasi-Ice Layer, QIL) (Figure 1-II, C) on some solid-state material (Figure 1-II, B), the arrangement of water molecules will be different from that of ice nuclei (Figure 1-I), and by taking advantage of this, they can suppress the growth and fusion of ice nuclei that adhere to the pseudo-ice layer and prevent the formation of ice blocks. The inventors predicted that the pseudo-ice layer would stop the growth of countless microscopic ice nuclei that cannot fuse with each other, and they would become crowded together on the pseudo-ice layer (Figure 1-III, D), which they believed would mean the formation of "thin ice" macroscopically. After extensive experiments, it was discovered that, even in high-humidity, low-temperature environments, no ice blocks form on the surface of the artificial ice layer formed on the layer of the present invention, but instead, thin ice forms, and that this thin ice is made up of countless tiny ice nuclei arranged in a uniform direction so as to be crowded together.Furthermore, it was confirmed that, even in high-humidity, low-temperature environments, repeated freezing and thawing of the thin ice does not produce ice blocks on the structure containing the layer, but instead, thin ice forms with good reproducibility, leading to the completion of the present invention.

[0013] Furthermore, the present disclosure reveals a coating (layer) of a solid-state substance and a support (structure) associated with the layer that allows thin ice to form consisting of aligned ice nuclei instead of ice blocks, even in high humidity and low temperature environments.

[0014] The arranged ice nuclei in the thin ice are typically thought to be two or more single crystals of ice arranged in contact with each other in the planar direction. Furthermore, the grain boundaries between the two or more single crystals are thought 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 from a direction perpendicular to the planar direction, where two or more ice nuclei are arranged, separated by a boundary line.

[0015] In a preferred embodiment, the layer is capable of forming ice nuclei having an average Feret diameter of 100 μm or less on its surface when it is kept for 1 minute under environmental conditions of an atmospheric pressure of 1,013 hPa, a humidity of 80±5% RH, and a temperature of 2±1° C., and then cooled to −8±1° C. under the same environmental conditions. The formation of ice nuclei having an average Feret diameter of 100 μm or less can suppress ice growth.

[0016] The average Feret 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, and may be, for example, 1 μm or more, or even 10 μm or more.

[0017] In this disclosure, the Feret diameter of the ice nuclei refers to the major axis of the rectangle circumscribing the ice nuclei. Also, in this disclosure, the average Feret diameter refers to the number average value of the Feret diameters measured for 10 or more ice nuclei.

[0018] In the present disclosure, the Feret diameter of ice nuclei can be measured by observing thin ice from a direction perpendicular to the planar direction using an optical microscope.

[0019] In a preferred embodiment, the layer is capable of forming ice nuclei having an average Feret diameter of 100 μm or less on its surface when cooled to −25±5° C. under environmental conditions of an atmospheric pressure of 1,013 hPa and a temperature of 20° C. to 25° C. By being able to form ice nuclei having an average Feret diameter of 100 μm or less, ice growth can be suppressed.

[0020] The average Feret 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, and may be, for example, 1 μm or more, or even 10 μm or more.

[0021] In a preferred embodiment, the layer can maintain the average Feret diameter of the ice nuclei at 100 μm or less when cooled to −25±5° C. to form ice nuclei under environmental conditions of an atmospheric pressure of 1,013 hPa and a temperature of 20° C. to 25° C., and then further maintained at −8±2° C. for 1 hour. The ability to form ice nuclei with an average Feret diameter of 100 μm or less can suppress ice growth.

[0022] The average Feret diameter of the ice nuclei after holding at −8±2° C. for 1 hour is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 50 μm or less, and may be, for example, 1 μm or more, or even 10 μm or more.

[0023] In a preferred embodiment, when the layer is kept for 1 minute under environmental conditions of an atmospheric pressure of 1,013 hPa, a humidity of 80±5% RH, and a temperature of 2±1°C, and then continuously cooled to -8±1°C and heated to 22±3°C under the same environmental conditions, thin ice composed of aligned ice nuclei can be formed over 95% or more of its surface. By forming thin ice over such an area ratio, ice growth can be suppressed over a wide area.

[0024] On the surface of the layer, the proportion of the area where thin ice composed of the arranged ice nuclei is formed is preferably 95% or more, more preferably 98% or more, and even more preferably 99% or more, but not more than 100%.

[0025] The presence or absence of the formation of thin ice composed of the aligned ice nuclei can be confirmed by observing the surface of the layer with an optical microscope.

[0026] In a preferred embodiment, when the layer is kept for 1 minute under environmental conditions of an atmospheric pressure of 1,013 hPa, a humidity of 80±5% RH, and a temperature of 2±1°C, and then cooled to −8±1°C under the same environmental conditions, thin ice having an average thickness of 1 mm or less can be formed on its surface. The formation of thin ice having an average thickness of 1 mm or less can suppress the growth of ice.

[0027] The average thickness of the thin ice is preferably 1 mm or less, more preferably 0.8 mm or less, and even more preferably 0.5 mm or less, and may be, for example, 1 μm or more, or even 10 μm or more.

[0028] In this disclosure, the thickness of the thin ice can be measured by observing the thin ice from a planar direction using an optical microscope. Also, in this disclosure, the average thickness of the thin ice means the number average of the measurements of the thickness of the thin ice measured at 10 or more locations.

[0029] In a preferred embodiment, the layer can form thin ice composed of aligned ice nuclei on its surface, and after the thin ice melts, can again form thin ice composed of aligned ice nuclei on its surface. That is, even after the thin ice has melted once, the layer can again form thin ice by cooling the layer. Furthermore, the layer can form thin ice even when repeatedly heated and cooled.

[0030] The number of times heating and cooling are repeated may be preferably one or more times, more preferably five or more times, and even more preferably eight or more times. The upper limit may be, for example, in accordance with the number of heating and cooling cycles in aluminum fins used in heat exchangers, and may be, for example, preferably 20,000 times or less, more preferably 10,000 times or less, and even more preferably 2,000 times or less.

[0031] In a preferred embodiment, when thin ice composed of aligned ice nuclei is formed on the surface of the layer, a portion or the entire surface is immersed in water for 120 hours, and thin ice composed of aligned ice nuclei is again formed 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. In other words, when thin ice composed of aligned ice nuclei is formed on the layer, the structure of the ice nuclei can be maintained even when the thin ice is immersed in water and placed under conditions that promote crystal growth. Therefore, ice crystal growth can be suppressed in the layer.

[0032] The same shape of the thin ice can be confirmed, for example, by checking that the rate of change in the average Feret diameter of ice nuclei in the thin ice is preferably 0% to 10%, more preferably 0% to 5%, and even more preferably 0% to 3%. The rate of change in the average Feret diameter of ice nuclei in the 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.

[0033] Furthermore, the same shape of the thin ice can be confirmed by the rate of change in the average thickness of the thin ice being preferably 0% to 10%, more preferably 0% to 5%, and even more preferably 0% to 3%. The rate of change in the average thickness of the thin ice may be calculated, for example, as (average thickness of the thin ice after immersion in water - average thickness of the thin ice before immersion in water) / average thickness of the thin ice before immersion in water.

[0034] In a preferred embodiment, the static contact angle of the layer measured at room temperature one second after water impact on the surface is preferably 30° to 100°, more preferably 31° to 99°, and even more preferably 32° to 98°. When the static contact angle is within this range, a pseudo-ice layer is formed on the surface, forming thin ice. As a result, the growth of ice (ice blocks) can be suppressed.

[0035] In the present disclosure, the static contact angle can be measured in accordance with JIS R 3257.

[0036] In a preferred embodiment, to form uniform thin ice, it is preferable that the water film of (over)cooled water before freezing present on the layer is uniform. The surface of the layer may preferably have a surface roughness index Ra (arithmetic mean roughness) value measured over a surface area of ​​30 μm in length and 30 μm in width of 0.001 μm or more and 1.500 μm or less. When the Ra value is within this range, the water film of (over)cooled water before freezing present on the surface of the layer becomes uniform, and thin ice with a uniform thickness is formed. As a result, the growth of ice (ice blocks) can be suppressed.

[0037] The surface roughness index Ra value may be 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.

[0038] In the present disclosure, the surface roughness index Ra value can be measured in accordance with ISO 25178.

[0039] In a preferred embodiment, the ratio of the amount of nitrogen atoms present on the surface of the layer divided by the amount of carbon atoms is 0.01 to 0.33. When the ratio is in this range, a pseudo-ice layer is formed on the surface, forming thin ice.

[0040] The ratio may be preferably 0.01 or more and 0.33 or less, more preferably 0.02 or more and 0.30 or less, and even more preferably 0.03 or more and 0.27 or less.

[0041] The ratio can be measured by X-ray photoelectron spectroscopy (XPS).

[0042] In a preferred embodiment, the layer of the present disclosure preferably contains a polymer having a functional group containing a nitrogen atom. By including a polymer having a functional group containing a nitrogen atom, water molecules can be randomly adsorbed on the layer surface, and the water molecules can have a crystalline arrangement different from that of a typical ice crystal phase (e.g., Ih phase). As a result, it is believed that ice crystal growth is suppressed, and the overall growth of ice is also suppressed.

[0043] Examples of the functional group containing a nitrogen atom include an amino group, an ammonium group, an imino group, an amide bond, and a nitrogen-containing heterocyclic group.

[0044] The amino group includes substituted or unsubstituted amino groups such as primary amino groups, secondary amino groups, and tertiary amino groups, and examples of the substituents of the amino group include C １－１０ Alkyl group and C １－１０ An example is an alkanol group.

[0045] The substituent of the ammonium group is, for example, C １－１０ Alkyl group and C １－１０ Examples of the ammonium group include an alkanol group, and examples of the counter base of the ammonium group include a halogen atom such as a chlorine atom.Specific examples of the ammonium group include trimethylammonium chloride, triethylammonium chloride, triethylammonium chloride, and trihydroxyethylammonium chloride.

[0046] The amide bond can be, for example, —NR １０ is a group represented by —CO—, and R １０ is a hydrogen atom or C１－２０ represents a hydrocarbon group. １０ C represented by １－２０ The hydrocarbon group is preferably C １－１０ alkyl group, more preferably C １－５ alkyl group, more preferably C １－３ It is an alkyl group.

[0047] The nitrogen-containing heterocyclic group may be either a monocyclic or polycyclic ring, and is preferably a 5- to 10-membered ring, more preferably a 5- to 9-membered ring, even more preferably a 5- or 6-membered ring, and still more preferably a 5-membered ring. Examples of the nitrogen-containing heterocyclic group include monocyclic and 5-membered nitrogen-containing heterocyclic groups such as a pyrrolidinyl group, a pyrrolyl group, an imidazolyl group, a pyralozyl group, an oxazolyl group, a thiazolyl group, an imidazolinyl group, a triazolyl group, and a tetrazolyl group; monocyclic 6-membered nitrogen-containing heterocyclic groups such as a piperidinyl group, a pyridinyl group, a morpholinyl group, a pyridazinyl group, a pyrimidinyl group, and a pyrazinyl group; and polycyclic nitrogen-containing ring groups such as an indolyl group, an isoindolyl group, a benzimidazolyl group, a purinyl group, a benzotriazolyl group, a quinolinyl group, an isoquinolinyl group, a quinazolyl group, and a quinoxalinyl group.

[0048] The nitrogen-containing heterocyclic group is preferably a five-membered nitrogen-containing heterocyclic group, more preferably an oxazolyl group.

[0049] The nitrogen atom-containing functional group may be preferably an amino group or a nitrogen-containing heterocyclic group, more preferably a primary and / or secondary amino group, or a nitrogen-containing heterocyclic group, even more preferably a primary and / or secondary amino group.

[0050] The polymer having a nitrogen atom-containing functional group is preferably a polymer having a nitrogen atom-containing functional group in the main chain and / or side chain, more preferably a polymer having one or more groups selected from an amino group, an ammonium group, an imino group, an amide bond, and a nitrogen-containing heterocyclic group in the main chain and / or side chain, still more preferably a polymer having an amino group or a nitrogen-containing heterocyclic group in the main chain and / or side chain, even more preferably a polymer having a primary and / or secondary amino group or a nitrogen-containing heterocyclic group in the main chain and / or side chain, still more preferably a polymer having a primary and / or secondary amino group in the main chain and / or side chain, and still more preferably a polymer having a primary and / or secondary amino group in the main chain and / or side chain.

[0051] Examples of the polymer having a functional group containing a nitrogen atom include (meth)acrylic (co)polymers, (meth)acrylamide (co)polymers, polyethyleneimine, and poly-L-lysine.

[0052] The polymer having a functional group containing a nitrogen atom is preferably a (meth)acrylic (co)polymer or a (meth)acrylamide (co)polymer from the viewpoints of mass productivity, economic efficiency, ease of handling, etc. The (meth)acrylic (co)polymer or (meth)acrylamide (co)polymer can be understood as a (meth)acrylic (co)polymer or (meth)acrylamide (co)polymer having a functional group containing a nitrogen atom.

[0053] The (meth)acrylic (co)polymer may be a (co)polymer of a monomer mixture containing a (meth)acrylic monomer, and the (meth)acrylamide (co)polymer may be a (co)polymer of a monomer mixture containing a (meth)acrylamide monomer. Monomers that may be contained in such a monomer mixture include unsaturated carboxylic acids, (meth)acrylic acid esters, hydroxy group-containing monomers, amino group-containing monomers, amide group-containing monomers, unsaturated carboxyammonium salts, unsaturated quaternary ammonium salts, vinyl ethers, vinyl esters, N-vinyl compounds, unsaturated alcohols, unsaturated amines, unsaturated sulfonic acids, and (meth)acrylonitrile.

[0054] Specific examples of monomers that can be contained in the monomer mixture include unsaturated carboxylic acids such as (meth)acrylic acid; (meth)acrylic acid esters 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, t-butylcyclohexyl (meth)acrylate, and hydroxymethylcyclohexyl (meth)acrylate; hydroxy group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; amino group-containing monomers such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and butylaminoethyl (meth)acrylate; aminoethyl(meth)acrylamide, dimethylaminomethyl(meth)acrylamide, methylaminopropyl(meth)acrylamide, and (meth)acrylic acid esters. 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 methallyl alcohol; unsaturated amines such as allylamine; unsaturated sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid; vinyl cyanides such as (meth)acrylonitrile and α-chloroacrylonitrile; aromatic group-containing monomers such as styrene and vinyltoluene; and nitrogen-containing heterocyclic group-containing monomers such as 2-vinyloxazoline, 4-methyl-2-vinyl-2-oxazoline and 5-methyl-2-vinyl-2-oxazoline.

[0055] The (meth)acrylic (co)polymer and (meth)acrylamide (co)polymer can be produced by polymerizing the monomer mixture. Such polymerization can be preferably carried out by any appropriate method, such as radical polymerization or anionic polymerization.

[0056] The weight average molecular weight of the (meth)acrylic (co)polymer and (meth)acrylamide (co)polymer may be 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. In the present disclosure, the weight average molecular weight may be measured by gel permeation chromatography and may be expressed as a polystyrene equivalent value.

[0057] In one embodiment, the total content of the (meth)acrylic (co)polymer having a functional group containing a nitrogen atom and the (meth)acrylamide (co)polymer may be preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably 95% by mass or more and 100% by mass or less, based on 100% by mass of the total polymer having a functional group containing a nitrogen atom.

[0058] The polyethyleneimine is a polymer having a repeating unit containing an amino group and an alkylene group, and the repeating unit is, for example, a repeating unit represented by the following formula: -(R １ -NH-) ｎ１ - (1) [In formula (1), R １ is C ２－１０ represents an alkylene group, and n1 represents an integer of 2 or more.

[0059] In formula (1), R １ is preferably C ２－５ Alkylene group, more preferably C ２－３ It may be an alkylene group.

[0060] The polyethyleneimine may be linear or branched, and the branched chains may be bonded to each other to form a cyclic structure.

[0061] The polyethyleneimine can be produced, for example, by ring-opening polymerization of a cyclic amine such as aziridine.

[0062] The weight average molecular weight of the polyethyleneimine may be 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.

[0063] The (meth)acrylic (co)polymer or (meth)acrylamide (co)polymer having a polyethyleneimine chain may be mentioned. Specific examples of the (meth)acrylic copolymer having a polyethyleneimine chain include "Polyment NK100PM," "Polyment NK-200PM," "Polyment NK-350," "Polyment NK-380," "Polyment KX-EK-100," "Polyment KX-EK-100R," "Polyment KX-EK-350," and "Polyment KX-EK-350R," all manufactured by Nippon Shokubai Co., Ltd.

[0064] Examples of the poly-L-lysine include α-poly-L-lysine and ε-poly-L-lysine.

[0065] The weight-average molecular weight of the poly-L-lysine may be preferably 1,000 or more and 30,000 or less, more preferably 3,000 or more and 20,000 or less, and even more preferably 4,500 or more and 15,000 or less. The weight-average molecular weight of the α-poly-L-lysine may be preferably 5,000 or more and 30,000 or less, more preferably 9,000 or more and 20,000 or less, and even more preferably 12,000 or more and 15,000 or less. The weight-average molecular weight of the ε-poly-L-lysine may be preferably 1,000 or more and 10,000 or less, more preferably 3,000 or more and 8,000 or less, and even more preferably 4,500 or more and 5,000 or less.

[0066] The polymer having a nitrogen atom-containing functional group preferably has a repeating unit having a nitrogen atom equivalent of 70 g / eq or less. The nitrogen atom equivalent may be 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. The repeating unit having a nitrogen atom equivalent of 70 g / eq or less may be the smallest repeating unit containing a nitrogen atom in the polymer having a nitrogen atom-containing functional group.

[0067] The acid value of the polymer having a nitrogen-containing functional group is preferably 100 mgKOH / g or less, more preferably 50 mgKOH / g or less, and even more preferably 20 mgKOH / g or less, and is 0 mgKOH / g or more. When the acid value of the polymer having a nitrogen-containing functional group is within this range, water molecules can be randomly adsorbed on the layer surface, and the water molecules can have a crystalline arrangement different from that of a typical ice crystal phase (e.g., Ih phase). As a result, it is thought that ice crystal growth is suppressed, and the overall growth of ice is also suppressed.

[0068] The weight average molecular weight of the polymer having a functional group containing a nitrogen atom may be 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.

[0069] In one embodiment, the proportion of the polymer having a functional group containing a nitrogen atom in the layer is preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably 95% by mass or more and 100% by mass or less, based on 100% by mass of the total layer. In another embodiment, the proportion of the polymer having a functional group containing a nitrogen atom in the layer is preferably 30% by mass or more and 95% by mass or less, more preferably 40% by mass or more and 90% by mass or less, and even more preferably 50% by mass or more and 85% by mass or less, based on 100% by mass of the total layer.

[0070] The layer may contain other additives in addition to the polymer having a nitrogen-containing functional group. Examples of such additives include thickeners, leveling agents, antifoaming agents, antistatic agents, antifogging agents, UV absorbers, radical scavengers, pigments, dyes, and fillers. The layer may further contain a compound having a polyalkylene glycol chain to adjust the surface wettability, and, if necessary, a crosslinking agent to fix the compound to the layer and / or the polymer having a nitrogen-containing functional group. Preferred polyalkylene glycol chains are polyethylene glycol chains and polypropylene glycol chains. Examples of compounds having a polyalkylene glycol chain include compounds having a hydroxyl group at the end of the polyalkylene glycol chain, compounds having an alkoxy group at the end of the polyalkylene glycol chain, and compounds having a glycidyl alkyl ether group at the end of the polyalkylene glycol chain.

[0071] Specific examples of compounds having a polyalkylene glycol chain 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 fatty acid glyceryl, polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, and polyoxyethylene sorbitol tetraoleate. , polyethylene glycol polypropylene glycol polyethylene glycol, polyoxyethylene stearylamine, polyoxyethylene oleylamine, polyoxyethylene alkylpropylene diamine, polyoxyethylene fatty acid monoethanolamide, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxypropylene diglyceryl ether, polyoxypropylene sorbitol, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxybutylene pentaerythritol ether, trimethylolpropane tris(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, and the like.The polymer having a functional group containing a nitrogen atom may also include a compound in which a compound containing a polyalkylene glycol chain is bonded to the functional group containing a nitrogen atom via a crosslinking agent.

[0072] Any crosslinking agent can be selected depending on the functional group of the compound having a polyalkylene glycol chain, but when the functional group is an OH group, an isocyanate compound is preferred, and specific examples include hexamethylene diisocyanate, hexamethylene diisocyanate trimer, 1,4-cyclohexyl diisocyanate, dicyclohexylmethane 4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and isophorone diisocyanate. These isocyanate groups may be blocked with a blocking agent such as 3,5-dimethylpyrazole, diethyl malonate, methyl ethyl ketoxime, or ε-caprolactam.

[0073] In one embodiment, the total amount of the compound having a polyalkylene glycol chain and the crosslinking agent is preferably 0% by mass or more and 99% by mass or less, more preferably 0% by mass or more and 75% by mass or less, and even more preferably 0% by mass or more and 50% by mass or less, relative to 100% by mass of the polymer having a functional group containing a nitrogen atom. The amount of the crosslinking agent is preferably 0% by mass or more and 50% by mass or less, more preferably 0% by mass or more and 40% by mass or less, and even more preferably 0% by mass or more and 30% by mass or less, relative to 100% by mass of the compound having a polyalkylene glycol chain.

[0074] In another embodiment, the total amount of the compound having a polyalkylene glycol chain and the crosslinking agent is preferably 10% by mass or more and 99% by mass or less, more preferably 20% by mass or more and 75% by mass or less, and even more preferably 25% by mass or more and 50% by mass or less, relative to 100% by mass of the polymer having a functional group containing a nitrogen atom. The crosslinking agent is preferably 1% by mass or more and 50% by mass or less, more preferably 3% by mass or more and 40% by mass or less, and even more preferably 5% by mass or more and 30% by mass or less, relative to 100% by mass of the compound having a polyalkylene glycol chain.

[0075] The thickness of the layer may be 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.

[0076] The method for forming the layer is not particularly limited. For example, the layer may be formed by a wet coating method or a dry coating method, preferably by a wet coating method. A layer formed by the wet coating method is also referred to as a coating film hereinafter.

[0077] In one embodiment, the layer can be produced by applying a solution containing the polymer having the nitrogen atom-containing functional group and additives as needed, and preferably can be formed by coating the solution by a wet coating method.

[0078] In the solution, the content of the polymer having a functional group containing a nitrogen atom can be selected arbitrarily depending on the coating method, but from the viewpoint of uniform coating property and ease of handling, it is preferably 0.01% by mass to 30% by mass, more preferably 0.05% by mass to 20% by mass, and even more preferably 0.1% by mass to 10% by mass. The arrangement and density of nitrogen atoms correlate with the ease of formation of a pseudo-ice layer and are also thought to be related to the formation of thin ice.

[0079] The solution may contain, as a solvent, water; lower alcohols such as ethanol, butanol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; glycols 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; esters such as ethyl acetate and butyl acetate, etc. Of these, water, lower alcohols, and glycols are preferred as the solvent, and water is more preferred.

[0080] Examples of wet coating methods include dip coating, spin coating, brush coating, flow coating, spray coating, roll coating, gravure coating and similar methods.

[0081] After the precursor film is obtained by applying a solution containing the polymer having a nitrogen-containing functional group and any additives used as needed, the precursor film may be dried as needed. By such drying, the solvent and the like can be removed.

[0082] The precursor layer may be dried at a temperature of preferably 0°C or higher and 200°C or lower, more preferably 5°C or higher and 180°C or lower, and even more preferably 10°C or higher and 150°C or lower, for a time of preferably 1 minute or higher and 10 hours or lower, more preferably 2 minutes or higher and 5 hours or lower, and even more preferably 3 minutes or higher and 3 hours or lower.

[0083] Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum deposition) include resistance heating, electron beam, high frequency heating using microwaves, etc., ion beam, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0084] (Second embodiment: membrane) The technical scope of the present disclosure also includes a membrane composed of water molecules, having a thickness of 20 Å or less, and not exhibiting the Ih phase under conditions of an atmospheric pressure of 1,013 hPa and a temperature of −8±1° C.

[0085] Ice growth can be suppressed on the surface of the film. That is, water molecules normally exhibit the Ih phase under conditions of an atmospheric pressure of 1,013 hPa and a temperature of -8±1°C. Therefore, it is believed that ice crystal growth is promoted on the surface of ice exhibiting the Ih phase. However, the film of the present disclosure does not exhibit the Ih phase, and the lattice arrangement of water molecules in the film is thought to be different from the lattice arrangement of water molecules in the Ih phase. Therefore, even if water molecules are adsorbed on the surface of the film, the water molecules do not contribute to the formation of ice crystals, and therefore it is thought that ice growth can be suppressed.

[0086] The thickness of the film may be 20 Å or less, preferably 3 Å or more and 20 Å or less.

[0087] In one embodiment, the film can be formed on the layer by holding the layer under environmental conditions of a pressure of 1,013 hPa, a humidity of 80±5% RH, and a temperature of 2±1°C for 1 minute, and then cooling the layer to −8±1°C under the same environmental conditions.

[0088] The present disclosure also includes a laminate comprising the above-described layer and a film disposed on the layer, wherein the film is composed of water molecules, has a thickness of 20 Å or less, and does not exhibit an Ih phase under conditions of a pressure of 1,103 hPa and a temperature of −8±1° C.

[0089] (Third embodiment: structure, member, and article) The technical scope of the present disclosure also includes a structure including a support and the layer. In the structure, the layer covers part or all of the surface of the support. With such a structure, ice growth can be suppressed on the surface.

[0090] The support usable in the present disclosure may be made of any suitable material, such as glass, resin (which may be a natural or synthetic resin, for example, a common plastic material), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., building materials, etc., sanitary products, etc.

[0091] In a preferred embodiment, the support may be made of a metal. Examples of such metals include Si, Al, Cu, Fe, Ni, and Zn, or alloys containing these. Examples of such alloys include, but are not limited to, Fe / Ni / Cr alloys and Al / Cu alloys. In a more preferred embodiment, the metal constituting the support may include Al, Cu, Fe, and SUS.

[0092] The shape of the support is not particularly limited and may be various shapes depending on the application. For example, the shape of the support may be a simple shape such as a plate or a rod, or may be a fin shape, an uneven shape, a porous structure, or the like to increase the surface area.

[0093] The layer has the same meaning as the layer in the first embodiment. The layer covers a part or the whole of the surface of the support. The layer is preferably disposed on the outermost surface of the structure.

[0094] The average thickness of the layer may be 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.

[0095] In a preferred embodiment, the structure further includes an adhesive layer disposed between the support and the layer. By providing such an adhesive layer, the adhesiveness between the support and the layer can be improved.

[0096] The adhesive layer is formed from a primer, which contains a coupling agent having an organic reactive group and a hydrolyzable silyl group in one molecule.

[0097] The concentration of the coupling agent may be, for example, 0.05% by mass or more, 0.1% by mass or more, or 0.5% by mass or more, relative to 100% by mass of the primer. The concentration of the coupling agent may be, for example, 100% by mass or less, 20% by mass or less, 10% by mass or less, or 5% by mass or less. In one aspect, the concentration of the coupling agent is, for example, 0.05% by mass or more and 100% by mass or less, relative to 100% by mass of the primer.

[0098] The coupling agent has an organic reactive group and a hydrolyzable silyl group in one molecule. These functional groups react with functional groups on the surface of the coating film (layer) shown in Figure 1 (B) and / or the support (A) shown in Figure 1 (A), respectively, to enhance adhesion between the coating film (layer) shown in Figure 1 (B) and the support (A).

[0099] The organic reactive 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, but may also be present in two or more. The organic reactive group is not particularly limited. Examples of the organic reactive group include at least one selected from the group consisting of an amino group, a glycidyl group, an epoxy group, a vinyl group, a methacrylic group, an acrylic group, a styryl group, a phenyl group, an isocyanate group, a blocked isocyanate group, and a mercapto group. The multiple organic reactive groups may be the same or different. The organic reactive group may be a glycidyl group, an epoxy group, an isocyanate group, or a blocked isocyanate group.

[0100] The hydrolyzable group (for example, (for example, at least one of the groups "B" in the general formula of the coupling agent described later, which constitutes a hydrolyzable silyl group together with the adjacent Si atom) may be present in one molecule of the coupling agent, or may be present in two or more, or may be present in three. The hydrolyzable group is not particularly limited as long as it is hydrolyzed to form a silanol group together with the adjacent Si atom. Examples of the hydrolyzable group include an alkoxy group, an acetoxy group, and a chlorine atom. The hydrolyzable group may be an alkoxy group. The alkoxy group may have 1 to 5 carbon atoms, 1 to 3 carbon atoms, or 1 or 2 carbon atoms. The coupling agent may have two or more alkoxy groups having 1 to 5 carbon atoms bonded to Si. The multiple hydrolyzable groups may be the same or different. The carbon chain of the alkoxy group may be linear or branched.

[0101] Specific examples of the hydrolyzable silyl group include a trimethoxysilyl group, a triethoxysilyl group, a tripropoxysilyl group, a tris(2-methoxyethoxy)silyl group, a dimethoxyalkylsilyl group, a diethoxyalkylsilyl group, a dipropoxyalkylsilyl group, and a bis(2-methoxyethoxy)alkylsilyl group. The hydrolyzable silyl group may be at least one of a trimethoxysilyl group and a triethoxysilyl group.

[0102] The coupling agent may be, for example, a compound represented by the following general formula: Ａ -RＣＰ ) ４－ｎｓ -Si-R Ｂ ｎｓ (In the formula, R Ａ At least one of R is the organic reactive group. Ｂ At least one of R is the hydrolyzable group. ＣＰ are each independently a single bond or a divalent organic group, and ns is an integer of 1 or more and 3 or less.

[0103] "-Si-R Ｂ ｎｓ " constitutes a hydrolyzable silyl group. In the above general formula, R other than the organic reactive group Ａ In the above general formula, R other than the hydrolyzable group may be, for example, a hydrogen atom. Ｂ may be, for example, a hydrocarbon group. ns may be 2 or more, and may be 3.

[0104] In the above general formula, R ＣＰ is a single bond or a divalent organic group, and may be a divalent organic group. ＣＰ For example, C １－６ Alkylene group, -(CH ２ ) ｃｐ１ -O-(CH ２ ) ｃｐ２ -(cp1 is an integer of 1 to 6, and cp2 is an integer of 1 to 6), or -phenylene-(CH ２ ) ｃｐ３ - (cp3 is an integer of 0 to 6). ＣＰ is C １－３ may be an alkylene group, ２－３ It may be an alkylene group, -CH ２ CH ２ CH ２ These groups may be, for example, fluorine atoms, C １－６ Alkyl group, C ２－６ alkenyl groups, and C ２－６ It may be substituted with one or more substituents selected from alkynyl groups.

[0105] Examples of coupling agents include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinylmethyldimethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-octanoylthio-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-dimethylbutylidene) Examples of the coupling agent include propylamine, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, "X-12-1195" manufactured by Shin-Etsu Chemical Co., Ltd., "X-12-1293" manufactured by Shin-Etsu Chemical Co., Ltd., and "X-12-1308ES" manufactured by Shin-Etsu Chemical Co., Ltd. One type of coupling agent may be used alone, or two or more types may be used in combination.

[0106] The primer may further contain other additives. Examples of the other additives include a thickener, a leveling agent, an antifoaming agent, an antistatic agent, an antifogging agent, an ultraviolet absorber, a radical scavenger, a pigment, a dye, and a filler. In particular, from the viewpoint of weather resistance, the primer may contain at least one of an ultraviolet absorber and a radical scavenger.

[0107] Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, triazine compounds, radical polymerizable compounds, and inorganic compounds. The ultraviolet absorber may be a triazine compound.

[0108] 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-octoxybenzophenone, 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'-carboxybenzophenone, 2-hydroxy-4-stearyloxybenzophenone, and 4,6-dibenzoylresortinol.

[0109] 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, and 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-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalimidomethyl)-5'-methylphenyl]benzotriazole, and 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol].

[0110] 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-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

[0111] Examples of radically polymerizable ultraviolet absorbers include 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acryloxybenzophenone, 2-hydroxy-5-methacryloxybenzophenone, 2-hydroxy-4-(acryloxy-ethoxy)benzophenone, 2-hydroxy-4-(methacryloxy-ethoxy)benzophenone, 2-hydroxy-4-(methacryloxy-diethoxy)benzophenone, 2-hydroxy-4-(acryloxy-triethoxy)benzophenone, 2-(2'-hydroxy-5'-methacryloxyethyl-3-tert-butylphenyl)-2H-benzotriazole, and 2-(2'-hydroxy-5'-methacrylyloxypropyl-3-tert-butylphenyl)-5-chloro-2H-benzotriazole.

[0112] 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.

[0113] Examples of the radical scavenger include hindered amine compounds.

[0114] Examples of the hindered amine light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethylpiperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxy]-2,2,6,6-tetramethylpiperidine, and bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate.

[0115] The (total) concentration of the ultraviolet absorber and / or radical scavenger is, for example, 1% by mass or more, optionally 2% by mass or more, or 3% by mass or more, relative to 100% by mass of the primer. The (total) concentration of the ultraviolet absorber and / or radical scavenger is, for example, 10% by mass or less, optionally 8% by mass or less, or optionally 6% by mass or less, relative to 100% by mass of the primer. In one aspect, the (total) concentration of the ultraviolet absorber and / or radical scavenger is 1% by mass or more and 10% by mass or less, relative to 100% by mass of the primer.

[0116] The primer may be diluted with an organic solvent. The organic solvent is not particularly limited. Examples of the organic solvent include lower alcohols such as ethanol, butanol, and isopropyl alcohol; 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. The adhesion layer may contain a compound having a moiety having affinity for the support and a moiety having affinity for the layer.

[0117] The average thickness of the adhesive layer may be preferably 0.001 μm or more and 20 μm or less, more preferably 0.01 μm or more and 15 μm or less, and even more preferably 0.05 μm or more and 10 μm or less.

[0118] The structure can be produced by forming the layer on the support, preferably by applying a solution containing the polymer having a nitrogen atom-containing functional group and an additive used as needed onto the support. The polymer having a nitrogen atom-containing functional group, the additive, the solution, and the method for applying the solution may be the same as those described in the first embodiment.

[0119] When the structure includes the adhesion layer, the structure can be produced by forming an adhesion layer on the support and then forming the layer on the adhesion layer. In this embodiment, the adhesion layer can be formed by a coating method such as a wet coating method. Examples of the wet coating method include dip coating, spin coating, flow coating, spray coating, roll coating, and gravure coating. The primer can be applied by spin coating.

[0120] The technical scope of the present disclosure also includes components comprising the above-described layer, such as heat transfer tubes, fins, valves, exterior materials, cover materials, and housings.

[0121] The technical scope of the present disclosure also includes articles containing the above-described components, such as thermal storage systems, heat exchangers, aircraft, ships, vehicles, electric wires, traffic lights, signs, billboards, residential roofs, solar panels, greenhouses, and power generation turbines.

[0122] The layers, films, structures, members, and articles of the present disclosure have been described in detail above. However, the layers, films, structures, members, and articles of the present disclosure, as well as their manufacturing methods, are not limited to those exemplified above.

[0123] The present disclosure provides a layer, film, structure, member, and article capable of suppressing ice growth, which may be suitably applied to thermal storage systems, heat exchangers, aircraft, ships, vehicles, electric wires, traffic lights, signs, billboards, residential roofs, solar panels, greenhouses, power generation turbines, and the like.

[0124] The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0125] <Water Contact Angle (Static Contact Angle)> The water contact angle (static contact angle) was measured using a contact angle meter, Drop Master 701, manufactured by Kyowa Interface Science Co., Ltd. Specifically, measurements were taken at five points on one test piece using a 2 μL water droplet, and the average value was used.

[0126] <Surface roughness (arithmetic mean roughness Ra)> The surface roughness (arithmetic mean roughness Ra) was measured using a laser microscope VK-9710 manufactured by Keyence Corporation. Specifically, Ra was measured in a 30 μm square surface area for image data acquired at a magnification of 150x objective lens. This was measured at six points, and the average value was used.

[0127] <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 measured by X-ray photoelectron spectroscopy (XPS). Using a photoelectron spectrometer PHI5000 VersaProbell manufactured by ULVAC-PHI, Inc., the peak areas of the N1s and C1s orbitals were observed and calculated under the following conditions: X-ray source: monochromated AIKα radiation (25 W); photoelectron detection area: 1,000 μm × 300 μm; photoelectron detection angle: 45 degrees; pass energy: 23.5 eV

[0128] [Example 1] To conduct a test using aluminum as a support, an A1050 aluminum plate (0.1 mm thick) was cut with a cutter to obtain aluminum pieces measuring 10 x 30 x 0.1 mm thick. The aluminum pieces were placed in a 50 ml centrifuge tube with acetone and then placed in an ultrasonic cleaner for 30 minutes to remove surface debris. The aluminum pieces were removed from the centrifuge tube and placed in a BIOFORCE NANOSCIENCES "Ozone Cleaner PC440" and irradiated with UV for 1 minute to further remove debris from the aluminum surface while simultaneously activating the negatively charged ions on the aluminum surface. A 10 wt% aqueous solution of active ingredient, previously prepared by diluting Nippon Shokubai Co., Ltd.'s "Polyment NK100PM" with distilled water, was applied to the activated aluminum pieces using an OSG System Products "Manual Bar Coater OSP-100" to form a coating film with a wet film thickness of 100 μm on the aluminum pieces. This aluminum piece was heated at 150°C for 3 minutes using a Yamato Scientific DX302 high-temperature dryer to obtain an aluminum test piece with a 10µm thick layer of Polyment NK100PM. The water contact angle on the surface of this test piece was 96°, the surface roughness Ra was 0.016µm, and the N / C ratio was 0.03.

[0129] Example 2: A Matsunami Glass Industrial Co., Ltd. "Round Microscope Cover Glass" (15 mm diameter) was placed in a BIOFORCE NANOSCIENCES Co., Ltd. "Ozone Cleaner PC440" and irradiated with UV for 1 minute to remove surface debris. Nippon Shokubai Co., Ltd.'s "Polyment NK100PM" was diluted with water to a concentration of 10 wt% active ingredient, and a wet coating film of 100 μm was prepared on the glass using an OSG System Products Co., Ltd. "Manual Bar Coater OSP-100 Model." The coating was then heated at 150°C for 3 minutes using a Yamato Scientific Co., Ltd. "DX302 Model High-Temperature Dryer" to obtain a glass specimen with a 10 μm-thick layer of Polyment NK100PM. The water contact angle on the surface of this specimen was 92°, the surface roughness Ra was 0.017 μm, and the N / C ratio was 0.03.

[0130] Example 3 A glass test piece having a 10 μm thick layer of poly-L-lysine hydrochloride was obtained by the same procedure as in Example 2, except that "Polyment NK100PM" was replaced with "Poly-L-lysine hydrochloride" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The water contact angle on the surface of this test piece was 64°, the surface roughness Ra was 1.159 μm, and the N / C ratio was 0.22.

[0131] Example 4 A glass test piece having a 10 μm-thick layer of ε-poly-L-lysine was obtained by the same procedure as in Example 2, except that "Polyment NK100PM" was replaced with "ε-poly-L-lysine 25% solution" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The water contact angle on the surface of this test piece was 33°, the surface roughness Ra was 0.337 μm, and the N / C ratio was 0.22.

[0132] Example 5 A glass test piece having a 10 μm thick layer of Epomin SP-200 was obtained by the same procedure as in Example 2, except that "Polyment NK100PM" was replaced with "Epomin SP-200" manufactured by Nippon Shokubai Co., Ltd. The water contact angle on the surface of this test piece was 34°, the surface roughness Ra was 0.012 μm, and the N / C ratio was 0.25.

[0133] [Comparative Example 1] An A1050 aluminum plate (thickness: 0.1 mm) was cut with a cutter to obtain aluminum pieces measuring 10 x 30 x 0.1 mm thick. The aluminum pieces were placed in a 50 ml centrifuge tube together with acetone, and then placed in an ultrasonic cleaner for 30 minutes to remove surface debris, yielding simple aluminum test pieces.

[0134] [Comparative Example 2] A1050 aluminum plate (0.1 mm thick) was cut with a cutter to obtain aluminum pieces measuring 10 x 30 x 0.1 mm thick. The aluminum pieces were placed in a 50 ml centrifuge tube with acetone, and then placed in an ultrasonic cleaner for 30 minutes to remove surface debris. The aluminum pieces were removed from the centrifuge tube and placed in a BIOFORCE NANOSCIENCES "Ozone Cleaner PC440" and irradiated with UV for 1 minute to further remove debris from the aluminum surface while simultaneously activating the negatively charged ions on the aluminum surface. Onto this activated aluminum piece, a solution of SIGMA-ALDRICH "polyacrylamide aqueous solution" (active ingredient 50 wt%, molecular weight 10,000) diluted with water to 40.0 wt% was applied using an OSG System Products "Manual Bar Coater OSP-25" to form a coating film with a wet film thickness of 25 μm on the aluminum piece. This aluminum piece was heated at 130°C for 3 minutes using a Yamato Scientific DX302 high-temperature dryer to obtain an aluminum test piece with a 10 μm-thick polyacrylamide layer. The water contact angle on the surface of this test piece was 17°, the surface roughness Ra was 0.018 μm, and the N / C ratio was 0.22.

[0135] Comparative Example 3: The same procedure as in Comparative Example 2 was carried out, except that the "polyacrylamide aqueous solution" was changed to "Ammonium Polyacrylate Solution 70-110" (active ingredient 42 wt %, molecular weight 10,000) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., to obtain an aluminum test piece having a 10 μm-thick layer of ammonium polyacrylate. The water contact angle on the surface of this test piece was 25°, the surface roughness Ra was 0.032 μm, and the N / C ratio was 0.04.

[0136] [Comparative Example 4] A round microscope cover glass (15 mm diameter) manufactured by Matsunami Glass Industry Co., Ltd. was placed in a BIOFORCE NANOSCIENCES Ozone Cleaner PC440 and irradiated with UV for 1 minute to remove surface debris. A 25 μm wet film was prepared on this glass using a Sigma-Aldrich polyacrylamide aqueous solution (active ingredient 50 wt%, molecular weight 10,000) diluted with water to 40.0 wt% using an OSG System Products manual bar coater OSP-25. The coating was then heated at 130 ° C. for 3 minutes using a Yamato Scientific DX302 high-temperature dryer to obtain a glass specimen with a 10 μm thick polyacrylamide layer. The contact angle of water on the surface of this test piece was 16°, the surface roughness Ra was 0.019 μm, and the N / C ratio was 0.24.

[0137] Comparative Example 5: A glass test piece having a 10 μm-thick layer of ammonium polyacrylate was obtained by the same procedure as in Comparative Example 4, except that the "polyacrylamide aqueous solution" was changed to "Ammonium Polyacrylate Solution 70-110" (active ingredient 42 wt %, molecular weight 10,000) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The contact angle of water on the surface of this test piece was 26°, the surface roughness Ra was 0.035 μm, and the N / C ratio was 0.04.

[0138] Ice Crystal Observation: As shown in Figure 2, Shin-Etsu Chemical Co., Ltd.'s "thermally conductive double-sided adhesive silicone tape TC-10SAS" was attached to the top surface of a Peltier-type temperature control unit (40 x 40 mm) inside a Japan High-Tech "10030" cooling and heating stage, and two test specimens were attached to the tape. This allowed the temperature of each test specimen to be freely adjusted between -40°C and room temperature with an accuracy of 0.1°C / min. This cooling and heating stage was then placed inside a Fukushima Galileo Co., Ltd. "EMU-0541" low-temperature incubator, with both test specimens positioned perpendicular to the ground. Approximately one hour after turning on the incubator, the temperature inside the chamber reached 2.0±1.0°C. A small fog generator containing a 1-liter bucket of water was then placed inside the incubator, and the device was activated to generate fog inside the chamber. This resulted in a humidity level of 80±5% inside the chamber after approximately two hours. This humidity was maintained throughout the ice crystal observation experiment by repeatedly turning on and off the fog generator. In this way, an environment of 2°C temperature and 80% humidity was created inside the low-temperature incubator.

[0139] Temperature Variable Program: The temperature program shown in Figure 3 was applied to a Japan High-Tech "10030 Model Cooling and Heating Stage" to vary the temperature of the test specimen attached to the Peltier temperature control unit between -8°C and 22°C. The minimum unit of this temperature variable program can be expressed by the following formula: [22°C (10 seconds) → Cooling (1 minute) → -8°C (27 minutes 50 seconds) → Heating (1 minute) →]. This program was repeated eight times continuously for a total of 240 minutes (4 hours) of experimentation. Observations were performed using an Apple iPad® mini. Video files of the changes on the test specimen captured using the device's camera function were used to analyze the changes on the test specimen as the temperature was varied. The iPad® mini's camera was positioned so that a clock placed to the right of the test specimen could be captured simultaneously (Figure 2). When the temperature variable program was started, this clock was set to 00:00 and operated to clarify the correspondence between the change in ice on the test piece and the temperature variable program.

[0140] Changes in Ice Over Time Figure 4 shows images, cut from the video and arranged from left to right, of water freezing on the surface of the test specimen at approximately 0, 1, 2, 3, 3.5, and 4 hours after starting the eight-time variable temperature program. A represents the test specimen of Comparative Example 1, and B represents the test specimen of Example 1. Both specimens were placed perpendicular to the ground in an environment with a temperature of 2°C and humidity of 80% (Figure 2). Condensation immediately formed on the surface of specimen A upon cooling to -8°C, and the condensed water transformed into ice with a rounded, curved, protruding surface. This ice continued to grow by absorbing the surrounding water for 27 minutes and 50 seconds while the temperature was maintained at -8°C. When heated to 22°C, it melted and turned into water droplets. These water droplets then remained in place without flowing off the test specimen, and when cooled again to -8°C, they transformed into larger ice blocks with rounded, protruding surfaces. This growth of the ice blocks progressed with each cycle of the variable temperature program. On the other hand, in the case of B, ice with rounded convex surfaces did not form, but instead a thin film of ice formed. This ice melted and ran down the coating. Each time the sample was cooled to -8°C using the variable temperature program, thin ice consisting of aligned ice nuclei formed with good reproducibility.

[0141] Figure 5 shows a schematic representation of ice formed on a test specimen as the temperature-variable program was executed. A represents the test specimen of Comparative Example 1, and B represents the test specimen of Example 1. Both specimens were placed in an environment with a temperature of 2°C and humidity of 80%. Ice with curved, convex surfaces formed on the surface of A, and its size increased with each cycle. The ice block formed on the surface approximately 240 minutes after eight cycles of cooling to -8°C is shown on the right side of A. Meanwhile, on the surface of B, ice nuclei whose crystal growth had been arrested were arranged. Macroscopically, this was observed as thin ice less than 1 mm thick. This thin ice melted upon heating to 22°C, forming droplets that ran down the surface of the test specimen. Thin ice consisting of arranged ice nuclei was formed with good reproducibility each time the test specimen was cooled to -8°C.

[0142] Figure 6 shows images of ice formed on each surface as the temperature-variable program was executed. A is the test piece of Comparative Example 2, and B is the test piece of Comparative Example 3. As the temperature-variable program of the cooling and heating stage progressed in an environment of 2°C temperature and 80% humidity, ice with curved, protruding surfaces formed on both coatings A and B, as shown in Figure 6, and its size increased with each run. Unlike the test piece of Comparative Example 1, the increase in ice size occurred below the test piece, and the mechanism behind this could be explained using Figure 5.

[0143] Figure 7 shows microscopic images of the ice formed on each test piece. A is a round microscope cover glass (15 mm diameter) manufactured by Matsunami Glass Industrial Co., Ltd., B is the test piece of Comparative Example 4, and C is the test piece of Comparative Example 5. The microscope used was an Olympus "Biological Microscope BX53" combined with a Japan High-Tech "10030 Model Cooling and Heating Stage." A 1 μL water droplet was placed on each test piece, and the freezing behavior was observed under the microscope.

[0144] When the cooling rate was set to -30°C / min and the stage temperature was lowered, the water droplets on both glasses went through a supercooled state and froze at around -25°C. At this frozen temperature, no aligned ice nuclei were observed in any of A to C. Nor were aligned ice nuclei observed when the temperature was changed to -8°C. Ice with curved protruding surfaces formed on A, and its thickness blocked the light from the microscope light source, causing parts of the microscope image to appear black. Ice with such protruding surfaces did not form on B and C, but no microscope images showing the alignment of ice nuclei were obtained.

[0145] Figure 8 shows microscopic images of ice formed on each test piece using the same procedure as in Figure 7. A represents the test piece of Example 2, B represents the test piece of Example 3, C represents the test piece of Example 4, and D represents the test piece of Example 5. When the cooling / heating stage was set to a cooling rate of -30°C / min and the temperature was lowered, all of the water droplets placed on the coatings of A to D went through a supercooled state and froze at around -25°C, turning into ice. The microscopic images of ice A to D shown in Figure 8 were observed at the moment of freezing. These images did not change even when the stage temperature was raised to -8°C. Furthermore, no change in the images was observed even after one hour while maintaining the temperature at -8°C. The microscopic images of A to D resemble an accumulation of brick blocks or crowded plant cells. In some cases, they exhibit patterns resembling fern leaves. These unique patterns are due to the regular arrangement of individual ice nuclei aligned in the same direction on the coating, and the resulting difference in refractive index between the basal and prism surfaces is observed as a boundary line. In other words, Figure 8 shows that the ice formed on A to D is composed of countless ice nuclei arranged close together with no gaps between them. Each ice nuclei would normally be a regular hexagon, but because the pseudo-ice layer cannot stop the growth of the six prism faces evenly, they take on a distorted shape. This result shows that the thin ice shown in Figure 4B and Figure 5B is composed of countless ice nuclei arranged in this way.

[0146] The present disclosure provides a layer, film, structure, member, and article capable of suppressing ice mass growth. Such layer, film, structure, member, and article may be preferably applied to thermal storage systems, heat exchangers, aircraft, ships, vehicles, electric wires, traffic lights, signs, billboards, residential roofs, solar panels, greenhouses, power generation turbines, etc.

Claims

1. A layer that is less than 1 millimeter thick and causes a thin layer of ice to form on its surface, consisting of aligned ice nuclei.

2. The layer according to claim 1, which, when kept for one minute under environmental conditions of an atmospheric pressure of 1,013 hPa, a humidity of 80±5% and a temperature of 2±1°C, and then cooled to -8±1°C under the same environmental conditions, forms ice nuclei on its surface having an average Feret's diameter of 100 μm or less.

3. The layer according to claim 1 or 2, which, when cooled to -25±5°C under environmental conditions of an atmospheric pressure of 1,013 hPa and a temperature of 20°C to 25°C, forms ice nuclei on its surface having an average Feret diameter of 100 μm or less.

4. The layer according to any one of claims 1 to 3, which can maintain the average Feret's diameter of the ice nuclei at 100 μm or less when the layer is cooled to -25±5°C under environmental conditions of an atmospheric pressure of 1,013 hPa and a temperature of 20°C to 25°C to form ice nuclei, and then further maintained at -8±2°C for 1 hour.

5. The layer according to any one of claims 1 to 4, which, when kept for 1 minute under environmental conditions of an atmospheric pressure of 1,013 hPa, a humidity of 80±5% RH and a temperature of 2±1°C, and then cooled to -8±1°C under the same environmental conditions, forms thin ice on its surface having an average thickness of 1 mm or less.

6. The layer according to any one of claims 1 to 5, which, when kept for one minute under environmental conditions of an atmospheric pressure of 1,013 hPa, a humidity of 80±5% and a temperature of 2±1°C, and then continuously cooled to -8±1°C and heated to 22±3°C under the same environmental conditions, forms thin ice composed of aligned ice nuclei over 95% or more of its surface.

7. A layer according to any one of claims 1 to 6, in which thin ice composed of aligned ice nuclei is formed on the surface, the thin ice is melted, and then thin ice composed of aligned ice nuclei is formed again on the surface.

8. A layer according to any one of claims 1 to 7, in which when thin ice composed of aligned ice nuclei is formed on a surface, a part or all of the surface is immersed in water for 120 hours, and thin ice composed of aligned ice nuclei is again formed on the surface, 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.

9. The layer according to any one of claims 1 to 8, wherein the static contact angle measured at room temperature on the surface of water one second after the water hits the surface is 30° or more and 100° or less.

10. The layer according to any one of claims 1 to 9, wherein the surface roughness index Ra value measured in an area 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.

11. The layer according to any one of claims 1 to 10, comprising a polymer having a functional group containing a nitrogen atom.

12. The layer according to any one of claims 1 to 11, comprising a polymer having a repeating unit with a nitrogen atom equivalent of 70 g / eq or less.

13. The layer according to any one of claims 1 to 12, wherein the ratio of the amount of nitrogen atoms present on the surface divided by the amount of carbon atoms is 0.01 or more and 0.33 or less.

14. The layer according to any one of claims 1 to 13, wherein the functional group containing a nitrogen atom is a primary and / or secondary amino group, or a nitrogen-containing heterocyclic group.

15. The layer according to any one of claims 1 to 14, wherein the polymer having a functional group containing a nitrogen atom contains a primary and / or secondary amino group, or a nitrogen-containing heterocyclic group in the main chain and / or side chain.

16. The layer according to any one of claims 1 to 15, wherein the polymer having a functional group containing a nitrogen atom is a (meth)acrylic (co)polymer or a (meth)acrylamide (co)polymer.

17. The layer according to any one of claims 1 to 16, wherein the acid value of the polymer having a functional group containing a nitrogen atom is 100 mgKOH / g or less.

18. The layer according to any one of claims 1 to 17, which is a coating.

19. A film composed of water molecules, having a thickness of 20 Å or less, and not exhibiting an Ih phase under conditions of an atmospheric pressure of 1,013 hPa and a temperature of -8±1°C.

20. A structure comprising a support and the layer according to any one of claims 1 to 18, said layer covering a part or all of the surface of said support.

21. The structure of claim 20, wherein the layer is disposed on an outermost surface of the structure.

22. The structure according to claim 20 or 21, further comprising an adhesive layer disposed between the support and the layer, the layer having an average film thickness of 0.001 μm or more and 20 μm or less, and the adhesive layer having an average film thickness of 0.001 μm or more and 20 μm or less.

23. A member comprising a layer according to any one of claims 1 to 18.

24. An article comprising the member of claim 23.

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