Layer and structure

Abstract

To suppress the growth of ice on a substrate.SOLUTION: A layer according to the present disclosure has a thickness of 1 millimeter or less and causes thin ice made from arrays of ice nuclei to form on the surface of the layer.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

[0002] It is known that certain polymers can suppress the growth of ice crystals in water and the formation of frost on a substrate. These polymers can be used as so-called ice crystal growth inhibitors or frost formation inhibitors in heat 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 functional group containing a nitrogen atom in the side chain. Patent Document 2 describes a frost formation inhibiting film containing an amphoteric polylysine derivative.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] Conventionally known compounds may not be 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.

Means for Solving the Problems

[0005] The present disclosure includes the following aspects. [1] A layer having a thickness of 1 millimeter or less and forming thin ice composed of arranged ice nuclei on its surface. [2] After being 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, the layer according to [1], which 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 forms 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. [4] The layer according to any one of [1] to [3], which can maintain the average Feret diameter of the ice nuclei at 100 μm or less when, after forming ice nuclei by cooling to -25 ± 5°C under environmental conditions of an atmospheric pressure of 1,013 hPa and a temperature of 20°C to 25°C, it is further held at -8 ± 2°C for 1 hour. [5] The layer according to any one of [1] to [4], which forms thin ice having an average film thickness of 1 mm or less on its surface when, after being 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, it is cooled to -8 ± 1°C under the same environmental conditions. [6] The layer according to any one of [1] to [5], which forms thin ice composed of arranged ice nuclei on 95% or more of its surface when, after being 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, continuous repetition of cooling to -8 ± 1°C and heating to 22 ± 3°C is continued under the same environmental conditions. [7] The layer according to any one of [1] to [6], which forms thin ice composed of arranged ice nuclei on its surface, dissolves the thin ice, and then forms thin ice composed of arranged ice nuclei on its surface again. [8] The layer according to any one of [1] to [7], in which when thin ice composed of arranged ice nuclei is formed on its surface, a part or the whole of the surface is immersed in water for 120 hours, and then thin ice composed of arranged ice nuclei is formed on its surface again, the shape of the thin ice formed after immersion in the water is the same as the shape of the thin ice formed before immersion in the water. [9] The layer according to any one of [1] to [8], wherein the static contact angle measured at 1 second after the impact of water at room temperature on the surface is 30° or more and 100° or less.

[10] The layer according to any one of [1] to [9], wherein the Ra value of the surface roughness index 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.

[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 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 [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] , which is a coating film.

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

[20] Comprising a support and the layer described in any one of [1] to

[18] or the film described in

[19] , The layer or film is a structure that covers part or all of the surface of the support.

[21] The layer is the structure described in

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

[22] Further comprising an adhesion layer disposed between the support and the layer, The average film thickness of the layer is 0.001 μm or more and 20 μm or less, The structure described in

[20] or

[21] , wherein the average film thickness of the adhesion layer is 0.001 μm or more and 20 μm or less.

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

[18] or the film described in

[19] .

[24] An article containing the member described in

[23] .

Advantages of the Invention

[0006] According to the layer and structure of the present disclosure, the growth of ice on a substrate can be suppressed.

Brief Description of the Drawings

[0007]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Mode for Carrying Out the Invention

[0008] (First Embodiment: Layer) The layer of the present disclosure forms thin ice on its surface, and the thin ice has a thickness of 1 millimeter or less and is composed of arranged ice nuclei.

[0009] In water that is almost frozen and cooled below 0°C, innumerable extremely small water molecule crystals called ice nuclei spontaneously occur (Figure 1-I). Ice is formed by these ice nuclei repeating crystal growth and random fusion to form a mass. When the freezing and melting of ice blocks are repeated in an environment with a relatively high humidity of about 80% and a low temperature of about 2°C, especially when its size increases. In this way, the generated ice blocks cause deterioration and damage to the support, and reduce the performance of various devices that utilize cold and heat, which has been a problem in the industrial and medical fields.

[0010] Certain polymers are known to suppress 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 the main chain and a functional group containing a nitrogen atom in the side chain suppresses the growth of ice nuclei in the solution. Further, Patent Document 2 describes that an amphoteric polylysine derivative coated on a support delays the time until the freezing of water starts on the coated surface. However, substances and methods for forming thin ice instead of ice blocks even in a high-humidity and low-temperature environment, which are important for suppressing the formation of ice blocks on a support, have not been clarified at all.

[0011] According to the layer of the present disclosure, the formation of ice blocks on a substrate can be suppressed. Preferably, even in a high-humidity and low-temperature environment, the formation of ice blocks on a support can be suppressed, and instead, thin ice composed of arranged ice nuclei can be formed. Further, even when the freezing and melting of thin ice are repeated in a high-humidity and low-temperature environment, thin ice can be reproducibly formed instead of ice blocks. The present disclosure should not be construed as being limited to a specific theory, but the reason why the layer of the present disclosure can exhibit such an effect is considered as follows. That is, the layer of the present disclosure has a thickness of 1 millimeter or less and has the ability to form thin ice composed of arranged ice nuclei on its surface. Since the thin ice is composed of arranged ice nuclei, crystal growth can be suppressed, and as a result, the growth of ice on the substrate is considered to be suppressed.

[0012] That is, the arrangement of water molecules that make up an ice nucleus (Figure 1-I) is strictly determined, and if there is a deviation from this arrangement, the ice nucleus cannot grow crystallographically. From this, the inventors thought that if a so-called Quasi-Ice Layer (QIL) (Figure 1-II, C) was formed on a substance in a solid state (Figure 1-II, B), by taking advantage of the fact that the arrangement of water molecules in the QIL is different from that of the ice nucleus (Figure 1-I), the growth and fusion of ice nuclei adhering to the QIL could be suppressed, and the formation of ice blocks could be prevented. The inventors predicted that countless extremely tiny ice nuclei, whose growth is stopped by the QIL and cannot fuse with each other, would be in a crowded state on the QIL (Figure 1-III, D), which they thought would mean that "thin ice" would be formed macroscopically. As a result of intensive experiments, it was found that on the surface of the QIL that can be formed on the layer of the present invention, even in a high-humidity and low-temperature environment, ice blocks are not formed, but instead thin ice is formed, and that the thin ice is an arrangement in which countless fine ice nuclei are aligned in the same direction. Furthermore, it was confirmed that even if the freezing and melting of the thin ice are repeated in a high-humidity and low-temperature environment, ice blocks are not formed on the structure including the layer, but instead thin ice is formed with good reproducibility, thus completing the present invention.

[0013] Further, according to the present disclosure, a solid-state substance coating (layer) that forms thin ice composed of ice nuclei arranged instead of ice blocks and a support (structure) including the layer can be clarified, even in a high-humidity and low-temperature environment.

[0014] The arranged ice nuclei in the above thin ice are typically considered to be arranged with two or more single crystals of ice in contact in a planar direction. Also, the grain boundaries between the two or more single crystals are considered to extend in a direction perpendicular to the planar direction. This can be confirmed, for example, when the thin ice is observed with an optical microscope from a direction perpendicular to the planar direction, and two or more ice nuclei are arranged separated by a boundary line.

[0015] In a preferred embodiment, after the above layer is 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, ice nuclei having an average Feret diameter of 100 μm or less can be formed on its surface. By being able to form ice nuclei having an average Feret diameter of 100 μm or less, the growth of ice can be suppressed.

[0016] The average Feret diameter of the above ice nuclei is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 50 μm or less, and may be, for example, 1 μm or more, and further 10 μm or more.

[0017] In the present disclosure, the Feret diameter of the above ice nuclei means the major axis of a rectangle circumscribing the above ice nuclei. Further, in the present disclosure, the above average Feret diameter means the number average value of the Feret diameters measured for 10 or more ice nuclei.

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

[0019] In a preferred embodiment, when the above 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, ice nuclei having an average Feret diameter of 100 μm or less can be formed on its surface. By being able to form ice nuclei having an average Feret diameter of 100 μm or less, the growth of ice can be suppressed.

[0020] The average Feret diameter of the above ice nuclei is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 50 μm or less, and may be, for example, 1 μm or more, and further 10 μm or more.

[0021] In a preferred embodiment, when the above layer is 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 held at -8 ± 2°C for 1 hour, the average Feret diameter of the ice nuclei can be maintained at 100 μm or less. By being able to form ice nuclei with an average Feret diameter of 100 μm or less, the growth of ice can be suppressed.

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

[0023] In a preferred embodiment, when the above layer is 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 the continuous repetition of cooling to -8 ± 1°C and heating to 22 ± 3°C is continued under the same environmental conditions, a thin ice composed of arranged ice nuclei can be formed on 95% or more of its surface. By being able to form thin ice at such an area ratio, the growth of ice can be suppressed over a wide range.

[0024] The ratio of the area where the thin ice composed of the arranged ice nuclei is formed on the surface of the above layer is preferably 95% or more, more preferably 98% or more, still more preferably 99% or more, and 100% or less.

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

[0026] In a preferred embodiment, when the above layer is 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, a thin ice with an average film thickness of 1 mm or less can be formed on its surface. By being able to form thin ice with an average film thickness of 1 mm or less, the growth of ice can be suppressed.

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

[0028] In the present disclosure, the film thickness of the glaze ice can be measured by observing the glaze ice from the planar direction using an optical microscope. Further, in the present disclosure, the average film thickness of the glaze ice means a value obtained by measuring the film thickness of the glaze ice at 10 or more locations and averaging the measured values.

[0029] In a preferred embodiment, the layer can form glaze ice composed of arranged ice nuclei on the surface, dissolve the glaze ice, and then form glaze ice composed of arranged ice nuclei on the surface again. That is, even after once dissolving the glaze ice, the layer can form glaze ice again by cooling the layer. The layer can further form glaze ice even when heating and cooling are repeated.

[0030] The number of repetitions of heating and cooling can preferably be 1 or more, more preferably 5 or more, still more preferably 8 or more, and the upper limit can be, for example, according to the number of heating and cooling cycles in aluminum fins used in heat exchangers, etc., and can preferably be 20,000 times or less, more preferably 10,000 times or less, still more preferably 2,000 times or less.

[0031] In a preferred embodiment, after forming glaze ice composed of arranged ice nuclei on the surface of the layer, when a part or the whole of the surface is immersed in water for 120 hours and then glaze ice composed of arranged ice nuclei is formed on the surface again, the shape of the glaze ice formed after the immersion in water can be the same as the shape of the glaze ice formed before the immersion in water. That is, when the layer forms glaze ice composed of arranged ice nuclei, even when the glaze ice is immersed in water and placed under conditions where crystal growth can be promoted, the structure of the ice nuclei can be maintained. Therefore, crystal growth of ice can be suppressed in the layer.

[0032] The fact that the shapes of the above-mentioned glaze ice are the same can be confirmed, for example, by the change rate of the average Feret diameter of the ice nuclei in the glaze ice being preferably 0% or more and 10% or less, more preferably 0% or more and 5% or less, and even more preferably 0% or more and 3% or less. The change rate of the average Feret diameter of the ice nuclei in the above-mentioned glaze ice can be calculated, for example, as (average Feret diameter in the glaze ice after immersion in water - average Feret diameter in the glaze ice before immersion in water) / average Feret diameter in the glaze ice before immersion in water.

[0033] Also, the fact that the shapes of the above-mentioned glaze ice are the same can be confirmed by the change rate of the average film thickness of the glaze ice being preferably 0% or more and 10% or less, more preferably 0% or more and 5% or less, and even more preferably 0% or more and 3% or less. The change rate of the average film thickness of the above-mentioned glaze ice can be calculated, for example, as (average film thickness of the glaze ice after immersion in water - average film thickness of the glaze ice before immersion in water) / average film thickness in the glaze ice before immersion in water.

[0034] In a preferred embodiment, on the surface, the static contact angle measured at the time of 1 second after the landing of water at room temperature can be preferably 30° or more and 100° or less, more preferably 31° or more and 99° or less, and even more preferably 32° or more and 98° or less. When the static contact angle is within such a range, a pseudo-ice layer is formed on the surface, and glaze ice is formed. As a result, the growth of ice (ice mass) 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, for uniform glaze ice formation, it is preferable that the water film of (super)cooled water before freezing present on the above-mentioned layer is uniform. On the surface, the Ra (arithmetic mean roughness) value of the surface roughness measured in a surface area of 30 μm in length and 30 μm in width can be preferably 0.001 μm or more and 1.500 μm or less. When the Ra value is within such a range, the water film of (super)cooled water before freezing present on the surface of the above-mentioned layer becomes uniform, and glaze ice with a uniform film thickness is formed. As a result, the growth of ice (ice mass) can be suppressed.

[0037] The Ra value, which is an index of the surface roughness, can preferably be 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 Ra value, which is an index of the surface roughness, can be measured in accordance with ISO 25178.

[0039] In a preferred embodiment, the layer can have a ratio of the amount of nitrogen atoms present on the surface to the amount of carbon atoms of 0.01 or more and 0.33 or less. When the ratio is within such a range, a pseudo-ice layer is formed on the surface, and thin ice is formed.

[0040] The ratio can preferably be 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 containing 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 crystal arrangement different from that of a typical ice crystal phase (for example, the Ih phase). As a result, it is considered that the crystal growth of ice is suppressed and the growth of the entire 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, a nitrogen-containing heterocyclic group, and the like.

[0044] Examples of the amino group include substituted or unsubstituted amino groups such as a primary amino group, a secondary amino group, and a tertiary amino group. Examples of the substituent of the amino group include a C 1-10 alkyl group and a C 1-10 alkanol group.

[0045] Examples of the substituent of the ammonium group include a C 1-10 alkyl group and a C 1-10 alkanol group. 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, trihydroxylethylammonium chloride, and the like.

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

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

[0048] Among the above nitrogen-containing heterocyclic groups, a 5-membered ring nitrogen-containing heterocyclic group is preferred, and an oxazolyl group is more preferred.

[0049] The functional group containing the nitrogen atom is 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, and still more preferably a primary and / or secondary amino group.

[0050] As the polymer having the functional group containing the nitrogen atom, a polymer having a functional group containing a nitrogen atom in the main chain and / or side chain is preferred, and a polymer containing one or more 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 is more preferred. A polymer having an amino group or a nitrogen-containing heterocyclic group in the main chain and / or side chain is still more preferred, a polymer containing a primary and / or secondary amino group or a nitrogen-containing heterocyclic group in the main chain and side chain is even more preferred, and a polymer having a primary and / or secondary amino group in the main chain and side chain is even more preferred.

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

[0052] From the viewpoints of mass productivity, economy, handleability, etc., as the polymer having the functional group containing the nitrogen atom, a (meth)acrylic (co)polymer or a (meth)acrylamide (co)polymer is preferred. The (meth)acrylic (co)polymer or the (meth)acrylamide (co)polymer can be understood as a (meth)acrylic (co)polymer or a (meth)acrylamide (co)polymer having a functional group containing a nitrogen atom.

[0053] The above (meth)acrylic (co)polymer can be a (co)polymer of a monomer mixture containing a (meth)acrylic monomer, and the above (meth)acrylamide (co)polymer can be a (co)polymer of a monomer mixture containing a (meth)acrylamide monomer. Examples of the monomers that can be included 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, (meth)acrylonitrile, and the like.

[0054] Specifically, examples of the monomers that may be included 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; other amide group-containing monomers such as aminoethyl (meth)acrylamide, dimethylaminomethyl (meth)acrylamide, methylaminopropyl (meth)acrylamide, (meth)acrylamide, N-methylol (meth)acrylamide, methoxybutyl (meth)acrylamide, and diacetone (meth)acrylamide; unsaturated carboxyammonium 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 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; nitrogen-containing heterocyclic group-containing monomers such as 2-vinyloxazoline, 4-methyl-2-vinyl-2-oxazoline, and 5-methyl-2-vinyl-2-oxazoline, and the like.

[0055] The above-mentioned (meth)acrylic (co)polymer and (meth)acrylamide (co)polymer can be produced by polymerizing the above monomer mixture. Such a polymerization method preferably includes radical polymerization and anionic polymerization, and can be carried out by any suitable method.

[0056] The weight average molecular weight of the above-mentioned (meth)acrylic (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. In the present disclosure, the weight average molecular weight can be measured by gel permeation chromatography and may be a polystyrene equivalent value.

[0057] In one aspect, the total content of the (meth)acrylic (co)polymer having a functional group containing a nitrogen atom and the (meth)acrylamide (co)polymer 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 in the total 100% by mass of the polymer having a functional group containing a nitrogen atom.

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

[0059] In formula (1), R 1 is preferably a C 2-5 alkylene group, more preferably a C 2-3 alkylene group.

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

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

[0062] The weight-average molecular weight of the above polyethyleneimine can preferably be 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] It may also be a (meth)acrylic (co)polymer or a (meth)acrylamide (co)polymer having the above polyethyleneimine chain. 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" manufactured by Nippon Shokubai Co., Ltd.

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

[0065] The weight-average molecular weight of the above poly-L-lysine can preferably be 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 above α-poly-L-lysine can preferably be 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. Also, the weight-average molecular weight of ε-poly-L-lysine can preferably be 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 functional group containing the nitrogen atom preferably has a repeating unit with a nitrogen atom equivalent of 70 g / eq or less. The nitrogen atom equivalent can preferably be 70 g / eq or less, more preferably 40 g / eq or more and 68 g / eq or less, and still more preferably 30 g / eq or more and 66 g / eq or less. The repeating unit with a nitrogen atom equivalent of 70 g / eq or less can be the smallest repeating unit containing a nitrogen atom in the polymer having a functional group containing the nitrogen atom.

[0067] The acid value of the polymer having a functional group containing the nitrogen atom is preferably 100 mgKOH / g or less, more preferably 50 mgKOH / g or less, and still more preferably 20 mgKOH / g or less, and is 0 mgKOH / g or more. When the acid value of the polymer having a functional group containing the nitrogen atom is in such a range, water molecules can be randomly adsorbed on the layer surface, and the water molecules can have a crystal arrangement different from that of a typical ice crystal phase (for example, Ih phase). As a result, it is considered that the crystal growth of ice is suppressed and the growth of the whole ice is also suppressed.

[0068] The weight average molecular weight of the polymer having a functional group containing the nitrogen atom can preferably be 1,000 or more and 1,000,000 or less, more preferably 3,000 or more and 500,000 or less, and still more preferably 5,000 or more and 200,000 or less.

[0069] In one aspect, the proportion of the polymer having a functional group containing the nitrogen atom in the above 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 still more preferably 95% by mass or more and 100% by mass or less in 100% by mass in total of the layer. In another aspect, the proportion of the polymer having a functional group containing the nitrogen atom in the above 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 still more preferably 50% by mass or more and 85% by mass or less in 100% by mass in total of the layer.

[0070] In addition to the polymer having a functional group containing a nitrogen atom, the above layer may contain other additives. Examples of such other additives include thickeners, leveling agents, defoaming agents, antistatic agents, antifogging agents, ultraviolet absorbers, radical scavengers, pigments, dyes, and fillers. The above layer may further contain a compound having a polyalkylene glycol chain for adjusting the wettability of the surface, and, if necessary, a crosslinking agent for fixing this to the layer and / or the polymer having a functional group containing a nitrogen atom. As the polyalkylene glycol chain, a polyethylene glycol chain and a polypropylene glycol chain are preferable. Examples of the compound having a polyalkylene glycol chain include a compound having a hydroxyl group at the end of the polyalkylene glycol chain, a compound having an alkoxy group at the end of the polyalkylene glycol chain, and a compound having a glycidyl alkyl ether group at the end of the polyalkylene glycol chain.

[0071] Specific examples of the compound 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, polyoxyethylene sorbitol tetraoleic acid, polyethylene glycol polypropylene glycol polyethylene glycol, polyoxyethylene stearylamine, polyoxyethylene oleylamine, polyoxyethylene alkyl propylene 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 the nitrogen atom may include a compound containing the polyalkylene glycol chain and a compound in which the compound containing the polyalkylene glycol chain is bonded to the functional group containing the nitrogen atom by a crosslinking agent.

[0072] The crosslinking agent can be arbitrarily selected according to the functional group of the compound having a polyalkylene glycol chain. When the functional group is an OH group, an isocyanate compound is preferable. Specific examples include hexamethylene diisocyanate, hexamethylene diisocyanate trimer, 1,4-cyclohexyl diisocyanate, 4,4'-dicyclohexylmethane 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 may preferably be 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 still more preferably 0% by mass or more and 50% by mass or less, based on 100% by mass of the polymer having a functional group containing the nitrogen atom. The crosslinking agent may preferably be 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 still more preferably 0% by mass or more and 30% by mass or less, based on 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 may preferably be 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 still more preferably 25% by mass or more and 50% by mass or less, based on 100% by mass of the polymer having a functional group containing the nitrogen atom. The crosslinking agent may preferably be 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 still more preferably 5% by mass or more and 30% by mass or less, based on 100% by mass of the compound having a polyalkylene glycol chain.

[0075] The thickness of the above layer can preferably be 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 above layer is not particularly limited. For example, the above layer can be formed by a wet coating method or a dry coating method, and preferably can be formed by a wet coating method. The layer formed by the wet coating method is also referred to as a coating film hereinafter.

[0077] In one aspect, the above layer can be produced by applying a solution containing a polymer having a functional group containing the above nitrogen atom and an additive used as required, and preferably can be formed by coating by a wet coating method using the solution.

[0078] In the above solution, the content of the polymer having a functional group containing the above nitrogen atom can be arbitrarily selected according to the coating method, but from the viewpoints of uniform coatability and handleability, it can preferably be 0.01% by mass or more and 30% by mass or less, more preferably 0.05% by mass or more and 20% by mass or less, and even more preferably 0.1% by mass or more and 10% by mass or less. The arrangement and existence density of nitrogen atoms are correlated with the ease of formation of a pseudo-ice layer and are also considered to be related to the formation of thin ice.

[0079] The above 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. Among them, as the solvent, water, lower alcohols, and glycols are preferred, and water is more preferred.

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

[0081] After applying a solution containing the polymer having the functional group containing the nitrogen atom and, if necessary, an additive used, it may be dried if necessary. By such drying, solvents and the like can be removed.

[0082] The drying of the precursor layer can preferably be carried out at a temperature of 0°C or higher and 200°C or lower, more preferably 5°C or higher and 180°C or lower, still more preferably 10°C or higher and 150°C or lower, and can preferably be carried out for a time of 1 minute or longer and 10 hours or shorter, more preferably 2 minutes or longer and 5 hours or shorter, still more preferably 3 minutes or longer and 3 hours or shorter.

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

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

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

[0086] The thickness of the above-mentioned film is 20 Å or less, and preferably can be 3 Å or more and 20 Å or less.

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

[0088] The present disclosure also includes a laminate including the above-mentioned layer and a film disposed on the above-mentioned layer, the film being a film composed of water molecules, having a thickness of 20 Å or less, and not exhibiting the Ih phase under the conditions of an atmospheric 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 above-mentioned layer. In the structure, the above-mentioned layer covers a part or all of the surface of the support. According to such a structure, the growth of ice can be suppressed on its surface.

[0090] Supports that can be used in the present disclosure can be composed of, for example, glass, resin (natural or synthetic resin, such as a general plastic material may be used), metal, ceramics, semiconductor (such as silicon, germanium, etc.), fiber (such as fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc., building members, sanitary products, and any suitable material.

[0091] In a preferred embodiment, the support may be made of metal. Such metals include Si, Al, Cu, Fe, Ni, or Zn, or alloys containing these. Such alloys are not particularly limited, and 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, and SUS.

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

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

[0094] The average film thickness of the 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.

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

[0096] The adhesion layer is formed from a primer. The primer 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, 0.5% by mass or more with respect 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, 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 with respect to 100% by mass of the primer.

[0098] The coupling agent has an organic reactive group and a hydrolyzable silyl group in one molecule. Each of these functional groups reacts with the functional groups on the surface of the B. coating film (layer) and / or the A. support described in FIG. 1 to enhance the adhesion between the B. coating film (layer) and the A. support.

[0099] The organic reactive group (for example, at least one of the groups "A" in the general formula of the coupling agent described later) may be one in one molecule of the coupling agent, or 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 methacryl group, an acrylic group, a styryl group, a phenyl group, an isocyanate group, a blocked isocyanate group, and a mercapto group. The plurality of organic reactive groups may be of the same kind or different kinds. 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, at least one of the groups "B" in the general formula of the coupling agent described below, which forms a hydrolyzable silyl group together with the adjacent Si atom) may be one, two or more, or three in one molecule of the coupling agent. The hydrolyzable group is not particularly limited as long as it is hydrolyzed to generate 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 number of carbon atoms of the alkoxy group may be 1 to 5, may be 1 to 3, or may be 1 or 2. The coupling agent may have two or more alkoxy groups having 1 to 5 carbon atoms bonded to Si. The plurality of 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 is, for example, represented by the following general formula: (R A -R CP ) 4-ns -Si-R B ns (In the formula, at least one of R A is the above organic reactive group, at least one of R B is the above hydrolyzable group, R 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.) is represented by.

[0103] “-Si-R B ns" constitutes a hydrolyzable silyl group. In the above general formula, R other than the organic reactive group A may be, for example, a hydrogen atom. In the above general formula, R other than the hydrolyzable group 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. R CP includes, for example, C 1-6 alkylene group, -(CH2) cp1 -O-(CH2) cp2 -(cp1 is an integer from 1 to 6, and cp2 is an integer from 1 to 6).) or -phenylene-(CH2) cp3 -(cp3 is an integer from 0 to 6).). R CP may be a C 1-3 alkylene group, may be a C 2-3 alkylene group, and may be -CH2CH2CH2-. These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group.

[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-acryloxypropylmethyldimethoxysilane, 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-dimethyl-butylidene)propylamine, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 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. The coupling agent is used alone or in combination of two or more.

[0106] The primer may further contain other additives. Examples of other additives include thickeners, leveling agents, defoamers, antistatic agents, antifogging agents, ultraviolet absorbers, radical scavengers, pigments, dyes, and fillers. Among them, in terms of weather resistance, the primer may contain at least one of an ultraviolet absorber and a radical scavenger.

[0107] Examples of ultraviolet absorbers include benzophenone-based compounds, benzotriazole-based compounds, triazine-based compounds, radically polymerizable compounds, and inorganic compounds. The ultraviolet absorber may be a triazine-based 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-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'-carboxybenzophenone, 2-hydroxy-4-stearyloxybenzophenone, and 4,6-dibenzoylresorcinol.

[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, 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, 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 radical 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'-methacryloyloxypropyl-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 radical scavengers include hindered amine compounds.

[0114] Examples of hindered amine light stabilizers 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-octyloxy-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, may be 2% by mass or more, and may be 3% by mass or more with respect 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, may be 8% by mass or less, and may be 6% by mass or less with respect to 100% by mass of the primer. In one embodiment, the (total) concentration of the ultraviolet absorber and / or radical scavenger is 1% by mass or more and 10% by mass or less with respect 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 including a site having an affinity for the support and a site having an affinity for the layer.

[0117] The average film thickness of the adhesion layer may preferably be 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 may be manufactured by forming the layer on the support, and preferably, may be manufactured by applying a solution including a polymer having a functional group containing the nitrogen atom and, if necessary, an additive used, onto the support. The polymer having a functional group containing the nitrogen atom, the additive, the solution, and the method of applying the solution may have the same meaning as the compound and the method described in the first embodiment.

[0119] When the above-described structure includes the above-described adhesion layer, such a structure can be manufactured by forming the adhesion layer on the upper part of the support and forming the above layer on the adhesion layer. In such an 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 may be applied by spin coating.

[0120] The technical scope of the present disclosure also includes a member including the above layer. Examples of the member including such a layer include a heat transfer tube, a fin, a valve, an exterior material, a cover material, and a housing.

[0121] The technical scope of the present disclosure also includes an article including the above member. Examples of such an article include a heat storage system, a heat exchanger, an aircraft, a ship, a vehicle, an electric wire, a traffic signal, a sign, a billboard, a residential roof, a solar panel, a greenhouse, and a power generation turbine.

[0122] The above layer, film, structure, member, and article of the present disclosure have been described in detail. Note that the layer, film, structure, member, and article of the present disclosure, as well as their manufacturing methods, etc. are not limited to those exemplified above.

[0123] According to the present disclosure, it is possible to provide a layer, film, structure, member, and article capable of suppressing the growth of ice. Such a layer, film, structure, member, and article can be preferably applied to a heat storage system, a heat exchanger, an aircraft, a ship, a vehicle, an electric wire, a traffic signal, a sign, a billboard, a residential roof, a solar panel, a greenhouse, a power generation turbine, etc.

Example

[0124] The present invention will be described more specifically by the following examples, but the present invention is not limited thereto.

[0125] <Contact angle of water (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, 5 measurements were made on 1 test piece using 2 μL of water droplets, and the average value was adopted.

[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, the Ra in a surface area of 30 μm square was measured for the image data obtained at a magnification of 150x of the objective lens. This was measured 6 times, and the average value was adopted.

[0127] <Ratio of nitrogen atoms / carbon atoms (N / C) present on the coating surface> The ratio of nitrogen atoms / carbon atoms present on the coating surface was measured by X-ray photoelectron spectroscopy (XPS). Using a "Photoelectron Spectrometer PHI5000VersaProbell" manufactured by ULVAC-PHI, Inc., the peak areas of the N1s and C1s orbits were observed and calculated under the following conditions. X-ray source: Monochromatized AlKα ray (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 the support, an A1050 aluminum plate (thickness 0.1 mm) was cut with a cutter to obtain aluminum pieces sized 10×30×0.1 mm in thickness. These aluminum pieces were placed in a 50 ml centrifuge tube together with acetone, and then this was subjected to ultrasonic cleaning for 30 minutes to remove dust on the surface. The aluminum pieces were taken out from this centrifuge tube and set in the "Ozone Cleaner PC440" manufactured by BIOFORCE NANOSCIENCES, and irradiated with UV for 1 minute to further remove dust on the aluminum surface and at the same time activate the negatively charged ions on the aluminum surface. An aqueous solution with an active ingredient of 10 wt% obtained by diluting "Poliment NK100PM" manufactured by Nippon Catalyst Co., Ltd. to 1 / 5 with distilled water in advance was applied onto this activated aluminum piece using the "Manual Bar Coater OSP-100 type" manufactured by OTSUKI SYSTEM PRODUCTS Co., Ltd., thereby producing a coating film with a Wet film thickness of 100 μm on the aluminum piece. This aluminum piece was heated at 150°C for 3 minutes using the "DX302 type high-temperature dryer" manufactured by Yamato Scientific Co., Ltd., to obtain an aluminum test piece with a layer of Poliment NK100PM with a thickness of 10 μm. The contact angle of water on the surface of this test piece was 96°, the surface roughness Ra was 0.016 μm, and N / C was 0.03.

[0129] [Example 2] "Microscope Cover Glass Round Type" (diameter 15 mm) manufactured by Matsunami Glass Industry Co., Ltd. was set in the "Ozone Cleaner PC440" manufactured by BIOFORCE NANOSCIENCES, and irradiated with UV for 1 minute to remove dust on the surface. Onto this glass, a diluted solution of "Poliment NK100PM" manufactured by Nippon Catalyst Co., Ltd. diluted with water to have an active ingredient of 10 wt% was used with the "Manual Bar Coater OSP-100 type" manufactured by OTSUKI SYSTEM PRODUCTS Co., Ltd. to produce a coating film with a Wet film thickness of 100 μm, and further heated at 150°C for 3 minutes using the "DX302 type high-temperature dryer" manufactured by Yamato Scientific Co., Ltd., to obtain a glass test piece with a layer of Poliment NK100PM with a thickness of 10 μm. The contact angle of water on the surface of this test piece was 92°, the surface roughness Ra was 0.017 μm, and N / C was 0.03.

[0130] [Example 3] The same procedures as in Example 2 were carried out except that “Polyment NK100PM” was changed to “Poly-L-lysine hydrochloride” manufactured by FUJIFILM Wako Pure Chemical Corporation, and a glass test piece having a layer of poly-L-lysine hydrochloride with a thickness of 10 μm was obtained. The contact angle of water on the surface of this test piece was 64°, the surface roughness Ra was 1.159 μm, and N / C was 0.22.

[0131] [Example 4] The same procedures as in Example 2 were carried out except that “Polyment NK100PM” was changed to “ε-Poly-L-lysine 25% solution” manufactured by Nippon Shokubai Co., Ltd., and a glass test piece having a layer of ε-poly-L-lysine with a thickness of 10 μm was obtained. The contact angle of water on the surface of this test piece was 33°, the surface roughness Ra was 0.337 μm, and N / C was 0.22.

[0132] [Example 5] The same procedures as in Example 2 were carried out except that “Polyment NK100PM” was changed to “Epomin SP-200” manufactured by Nippon Catalyst Co., Ltd., and a glass test piece having a layer of Epomin SP-200 with a thickness of 10 μm was obtained. The contact angle of water on the surface of this test piece was 34°, the surface roughness Ra was 0.012 μm, and N / C was 0.25.

[0133] [Comparative Example 1] An A1050 aluminum plate (thickness: 0.1 mm) was cut with a cutter to obtain an aluminum piece having a size of 10 × 30 × thickness 0.1 mm. This aluminum piece was placed in a 50-ml centrifuge tube together with acetone, and then this was subjected to ultrasonic cleaning for 30 minutes to remove dust on the surface, obtaining a simple aluminum test piece.

[0134] [Comparative Example 2] An A1050 aluminum plate (thickness 0.1 mm) was cut with a cutter to obtain aluminum pieces sized 10×30×0.1 mm in thickness. These aluminum pieces were placed in a 50 ml centrifuge tube together with acetone, and then this was subjected to ultrasonic cleaning for 30 minutes to remove surface dust. The aluminum pieces were taken out from this centrifuge tube and set in the "Ozone Cleaner PC440" manufactured by BIOFORCE NANOSCIENCES, and irradiated with UV for 1 minute to further remove surface dust of the aluminum and at the same time activate the negatively charged ions on the aluminum surface. Onto this activated aluminum piece, an aqueous solution obtained by diluting the "aqueous polyacrylamide solution" (active ingredient 50 wt%, molecular weight 10,000) manufactured by SIGMA-ALDRICH with water to 40.0 wt% was applied using the "manual bar coater OSP-25 type" manufactured by Otsuka Chemical Co., Ltd., 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 the "DX302 type high-temperature dryer" manufactured by Yamato Scientific Co., Ltd., 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 N / C was 0.22.

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

[0136] [Comparative Example 4] A "round cover glass for microscope" (diameter 15 mm) manufactured by Matsunami Glass Industry Co., Ltd. was set in an "ozone cleaner PC440" manufactured by BIOFORCE NANOSCIENCES, and UV was irradiated for 1 minute to remove dust on the surface. On this glass, a product of SIGMA-ALDRICH's "aqueous polyacrylamide solution" (active ingredient 50 wt%, molecular weight 10,000) diluted with water to 40.0 wt% was used with a "manual bar coater OSP-25 type" manufactured by OTSUKI SYSTEM PRODUCTS Co., Ltd. to prepare a coating film with a Wet film thickness of 25 μm, and further heated at 130 °C for 3 minutes using a "DX302 type high-temperature dryer" manufactured by Yamato Scientific Co., Ltd. to obtain a glass test piece 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 N / C was 0.24.

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

[0138] Observation of ice crystals As shown in Fig. 2, a "Thermal Conductive Double-Sided Adhesive Silicon Tape TC-10SAS" manufactured by Shin-Etsu Chemical Co., Ltd. was pasted on the upper surface of a Peltier type temperature control unit (40×40 mm) inside the "Model 10030 Cooling and Heating Stage" manufactured by Japan High-Tech Co., Ltd., and two test pieces were pasted on it. By doing so, it became possible to freely change the temperature of each test piece between -40°C and room temperature with an accuracy of 0.1°C / min. This cooling and heating stage was placed inside an "EMU-0541 Type Low-Temperature Incubator" manufactured by Fushimagarirei Co., Ltd., and the two test pieces were installed so that both were perpendicular to the ground. The temperature inside the incubator could be set to 2.0 ± 1.0°C about 1 hour after turning on the power of the incubator. Then, a water bucket of about 1 liter with a smaller fog generator inserted was placed inside the incubator, and the fog generator was operated to generate fog inside the incubator. As a result, the humidity inside the incubator could be set to 80 ± 5% about 2 hours later. By repeating the start and stop of the fog generator, this humidity was maintained throughout the ice crystal observation experiment. In this way, an environment with a temperature of 2°C and a humidity of 80% was created inside the low-temperature incubator.

[0139] Temperature Variable Program By applying the temperature program shown in Fig. 3 to the "Model 10030 Cooling and Heating Stage" manufactured by Japan High-Tech Co., Ltd., the temperature of the test piece attached to the Peltier type temperature control unit was changed 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) →] When this program was continuously repeated 8 times for a total of 240 minutes (4 hours) of experiments, we observed what kind of ice was formed on the surface of the test piece and how the ice melted. For the observation, we used the "iPad (registered trademark) mini" manufactured by Apple. Using the video file that captured the changes on the test piece with the camera function of this product, we analyzed the changes on the test piece with the variable temperature. The position of the camera of the "iPad (registered trademark) mini" was adjusted so that the clock placed on the right side of the test piece could be photographed simultaneously (Figure 2). When the variable temperature program was started, this clock was set to 00:00 and operated to clarify the correspondence between the changes in the ice on the test piece and the variable temperature program.

[0140] Changes in ice over time Figure 4 shows the images of the test piece surface when water was frozen at approximately 0, 1, 2, 3, 3.5, and 4 hours after starting the above-mentioned variable temperature program 8 times in total, cut out from the video and arranged from left to right. A is the test piece of Comparative Example 1, and B is the test piece of Example 1. Both are in a state of being placed vertically on the ground in an environment of temperature 2°C and humidity 80% (Figure 2). The surface of A immediately condensed with the cooling to -8°C, and the condensed water changed into ice with a round and bulging curved protruding surface. This ice continued to grow by adsorbing the surrounding water during the 27 minutes and 50 seconds when -8°C was maintained, and melted into water droplets when heated to 22°C. And these water droplets remained at the place without flowing down from the test piece, and changed into ice cubes with a larger and rounder protruding surface when cooled to -8°C again. Such growth of ice cubes progressed with each cycle of the variable temperature program. On the other hand, for B, ice with a round protruding surface was not formed. Instead, thin film-like ice was formed. This ice flowed down on the coating film simultaneously with melting. Each time it was cooled to -8°C by the variable temperature program, thin ice composed of arranged ice nuclei was formed with good reproducibility every time.

[0141] Figure 5 schematically shows the ice formed on the test piece as the temperature variable program is executed. A is the test piece of Comparative Example 1, and B is the test piece of Example 1. Both are in a state of being placed in an environment with a temperature of 2°C and a humidity of 80%. Ice with a curved protrusion was formed on the surface of A, and its size increased with each cycle. The ice block formed on the surface after about 240 minutes of repeating the cooling to -8°C eight times is shown at the right end of A. On the other hand, ice nuclei with crystal growth stopped were arranged on the surface of B. Macroscopically, this was observed as thin ice with a thickness of 1 mm or less. Such thin ice melted as the temperature was raised to 22°C and flowed down the surface of the test piece as water droplets. The thin ice composed of the arranged ice nuclei was reproducibly formed each time the cooling to -8°C was repeated.

[0142] Figure 6 shows images of the ice formed on each surface as the temperature variable program is 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 progresses in an environment with a temperature of 2°C and a humidity of 80%, ice with a curved protrusion is formed on both coatings of A and B as shown in Figure 6, and their sizes increase with each cycle. Different from the case of the test piece of Comparative Example 1, the increase in the size of the ice occurred below the test piece, but the mechanism could be explained using Figure 5.

[0143] Figure 7 is a microscopic image of the ice formed on each test piece. A is a round microscope cover glass (diameter 15 mm) manufactured by Matsunami Glass Industry 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 the "Biological Microscope BX53" manufactured by Olympus Corporation, which was combined with the "10030 Type Cooling and Heating Stage" manufactured by Japan High-Tech Corporation. A 1 μL water droplet was placed on each test piece, and the state when it froze was observed under the microscope.

[0144] When the cooling rate was set to -30 °C / min and the temperature of the stage was decreased, water droplets on any of the glasses froze at around -25 °C after passing through the supercooled state. At this freezing temperature, no ice nuclei arranged in any of A to C were observed. Also, no arranged ice nuclei were observed when these temperatures were changed to -8 °C. Ice with a curved protruded surface was formed in A, and since the light from the microscope light source was blocked by its thickness, a part of the microscope image appeared black. Such ice with a protruded surface was not formed in B and C, and no microscope image showing the arrangement of ice nuclei was obtained at all.

[0145] Figure 8 is a microscope image of ice generated on each test piece by performing the same operation as in Figure 7. 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 / min and the temperature was decreased, all water droplets placed on the coatings of A to D froze and changed to ice after passing through the supercooled state at around -25 °C. The microscope images of the ice of A to D shown in Figure 8 were observed at the moment of freezing. These images did not change even when the temperature of the stage was raised to -8 °C. Furthermore, no change in the images was observed even after 1 hour while maintaining -8 °C. The microscope images of A to D look like either an accumulation of bricks or crowded plant cells. It may exhibit a pattern like that of a fern leaf. The reason such unique patterns can be seen is that individual ice nuclei are regularly arranged with their directions aligned on the coating, and as a result, the difference in refractive index between the basal plane and the prism plane is observed as a boundary line. That is, Figure 8 shows that the ice generated on A to D is composed of innumerable ice nuclei arranged without gaps as if crowded together. Individual ice nuclei would originally exhibit a regular hexagon, but since the pseudo-ice layer cannot evenly stop the growth of the six prism planes, they become distorted in shape. This result shows that the thin ice shown in B of Figure 4 and B of Figure 5 is composed of such innumerable arranged ice nuclei.

Industrial Applicability

[0146] According to the present disclosure, it is possible to provide a layer, film, structure, member, and article capable of suppressing the growth of ice cubes. Such a layer, film, structure, member, and article can be preferably applied to a heat storage system, a heat exchanger, an aircraft, a ship, a vehicle, an electric wire, a traffic signal, a sign, a billboard, a residential roof, a solar panel, a greenhouse, a power generation turbine, and the like.

Claims

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

2. 2. The layer according to claim 1, 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 ice nuclei on its surface having an average Feret's diameter of 100 μm or less.

3. 2. The layer according to claim 1, 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 claim 1, wherein the layer can maintain the average Feret 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. 2. The layer according to claim 1, 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 film thickness of 1 mm or less.

6. 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 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 claim 1 , wherein 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. 2. The layer described in claim 1, wherein 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. 2. The layer according to claim 1, wherein the static contact angle of water measured at room temperature on the surface 1 second after impact is in the range of 30° to 100°.

10. 2. The layer according to claim 1, wherein the surface roughness index Ra value measured in an area of ​​30 μm length by 30 μm width on the surface is 0.001 μm or more and 1.500 μm or less.

11. The layer of claim 1 comprising a polymer having functional groups that contain nitrogen atoms.

12. 2. The layer of claim 1 comprising a polymer having repeat units with a nitrogen atom equivalent of 70 g / eq or less.

13. 2. The layer according to claim 1, 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 claim 1 , 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 claim 1 , 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 in the side chain.

16. The layer according to claim 1 , 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 claim 1 , wherein the polymer having a functional group containing a nitrogen atom has an acid value of 100 mg KOH / g or less.

18. The layer of claim 1 which is a coating.

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

20. A support and a layer according to any one of claims 1 to 18, A structure in which the layer covers a part or the entire surface of the support.

21. 21. The structure of claim 20, wherein the layer is disposed on a top surface of the structure.

22. The film further includes an adhesive layer disposed between the support and the layer, The average thickness of the layer is 0.001 μm or more and 20 μm or less, The structure according to claim 20 , wherein the average thickness of the adhesion layer is 0.001 μm or more and 20 μm or less.

23. A component 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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