CN113710473A

CN113710473A - Structure, method for manufacturing structure, member for heat exchanger, and heat exchanger

Info

Publication number: CN113710473A
Application number: CN202080029257.3A
Authority: CN
Inventors: 植野纯平; 铃木秀也; 高野启; 都玹姃
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2019-04-18
Filing date: 2020-04-07
Publication date: 2021-11-26
Also published as: JPWO2020213485A1; WO2020213485A1; JP7031790B2; KR20210132113A

Abstract

Provided is a structure having excellent water repellency and water sliding properties. Specifically disclosed is a structure having a water-repellent slip layer on a substrate, wherein the water-repellent slip layer comprises: a polymer having a polyethyleneimine skeleton, a fluorine-containing compound, and a silicon-containing substance.

Description

Structure, method for manufacturing structure, member for heat exchanger, and heat exchanger

Technical Field

The invention relates to a structure, a method of manufacturing the structure, a member for a heat exchanger, and a heat exchanger.

Background

Heat exchangers are used in air conditioners, coolers (refrigerators, freezers), electric vehicles, and the like. In this heat exchanger, a member having high thermal conductivity is used to efficiently perform heat exchange in a small space, and a structure is adopted in which the surface area per unit volume is increased as much as possible. Therefore, in the heat exchanger, fins are generally used in which aluminum plates having high thermal conductivity, light weight, and excellent workability are arranged in parallel at narrow intervals.

When the temperature of the fin surface is equal to or lower than the dew point during operation of the apparatus including the heat exchanger described above, water droplets (dew condensation water) may adhere to the fin surface. In particular, when the apparatus including the heat exchanger is an outdoor unit of an air conditioner and is in a heating operation, dew condensation water on the surface of the fins freezes due to a low atmospheric temperature, and the frozen ice forms nuclei to generate frost. The ventilation resistance is increased by frost on the surface of the fin, and thus there is a problem that the heat exchange efficiency of the heat exchanger is significantly reduced.

As a method for suppressing dew condensation water and frost on the surface of the heat dissipating sheet, there is a method for forming a hydrophilic coating film on the surface of the heat dissipating sheet. By making the heat sink hydrophilic, the dew condensation water adhering to the heat sink is uniformly diffused on the surface of the heat sink, and the dew condensation water can be dropped by the lubricity of the heat sink. However, even when the heat sink is made hydrophilic, adhesion of dew condensation water itself cannot be prevented.

As another method for suppressing dew condensation water and frost on the surface of the heat dissipating sheet, there is a method for forming a water repellent coating film on the surface of the heat dissipating sheet. The dew condensation water on the surface of the heat dissipating fin can be repelled by setting the heat dissipating fin to be water repellent. However, the water repellency of the fin surface does not necessarily correlate with the water-slipping property of the fin surface, and even in the case of a water-repellent fin, the water-slipping property of the fin is insufficient, and therefore dew condensation water may not be sufficiently removed.

Methods of forming an uneven shape on the surface of the heat sink itself or forming an uneven shape by attaching water repellent fine particles to the surface of the heat sink have also been studied (patent documents 1 to 3), but removal of dew condensation water and frost is insufficient.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2013-147573

Patent document 2: japanese patent laid-open publication No. 2013-36733

Patent document 3: japanese patent laid-open publication No. 2013-103414

Disclosure of Invention

Problems to be solved by the invention

The problem to be solved by the present invention is to provide a structure having excellent water repellency and water sliding property.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a layer containing a polymer having a polyethyleneimine skeleton, a fluorine-containing compound, and a silicon-containing substance on a substrate can exhibit both water repellency and water slipping property, thereby completing the present invention.

As a result of intensive studies to solve the above problems, the present inventors have found that a layer in which a fibrous silicon-containing substance having a nanometer order is present on a substrate and the surface of the substrate is covered with a turf-like substance or a layer in which the surface of the substrate is covered with a silicon-containing substance having a network structure having a nanometer order exhibits both water repellency and water slipping property, and have completed the present invention.

That is, the present invention relates to a structure having a water-repellent slip layer on a substrate, the water-repellent slip layer comprising: a polymer having a polyethyleneimine skeleton, a fluorine-containing compound, and a silicon-containing substance.

That is, the present invention relates to a structure having a slide-down water-repellent layer on a base material, wherein the slide-down water-repellent layer includes a fluorine-containing compound and a silicon-containing substance, and the surface of the base material is covered with a nano-scale fibrous silicon-containing substance in a turf-like manner or with a nano-scale network-structured silicon-containing substance.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a structure excellent in both water repellency and water slipping property can be provided.

Drawings

Fig. 1 is an SEM photograph of an aluminum flat plate having a layer of a polyethyleneimine polymer covered with a silicon-containing substance, produced in example 1.

Fig. 2 SEM photograph of an aluminum flat plate having a layer of a polyethyleneimine polymer covered with a silicon-containing substance, produced in example 1.

Fig. 3 is a schematic diagram showing an embodiment of a heat exchanger using the structure of the present invention.

Detailed Description

Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within a range not impairing the effects of the present invention.

< Structure >

The structure of the present invention is a laminate comprising a base material and a slip-off water-repellent layer, the slip-off water-repellent layer having on the base material: a polymer having a polyethyleneimine skeleton, a fluorine-containing compound, and a silicon-containing substance.

In the structure of the present invention, the layer containing the polymer having a polyethyleneimine skeleton, the fluorine-containing compound, and the silicon-containing substance can simultaneously exhibit both high water repellency and high water slipping property with respect to water.

Hereinafter, each element of the structure of the present invention will be described.

[ base Material ]

The substrate of the structure of the present invention is not particularly limited, and for example, a substrate containing a metal (metal substrate), a substrate containing a resin (resin substrate), or the like can be used.

Examples of the metal constituting the metal base include iron, copper, aluminum, stainless steel, zinc, silver, gold, platinum, and alloys thereof. Among these, aluminum, copper, or an alloy thereof is preferable, and aluminum or an aluminum alloy is more preferable.

Examples of the resin constituting the resin base include polyethylene, polypropylene, polycarbonate, polyester, polystyrene, polymethacrylate, polyvinyl chloride, polyvinyl alcohol, polyimide, polyamide, polyurethane, epoxy resin, cellulose resin, and the like.

The substrate may be subjected to surface treatment such as etching treatment, plasma treatment, ozone treatment, or the like.

The shape of the base material is not particularly limited, and examples thereof include a flat plate shape, a curved surface shape, and the like, and any shape can be used depending on the application.

When the substrate is in the form of a flat plate, the thickness thereof is not particularly limited, and is, for example, 10 to 1000 μm, preferably 50 to 500 μm.

[ slip Water-repellent layer ]

The slip-down water repellent layer of the structure of the present invention comprises: a polymer having a polyethyleneimine skeleton, a fluorine-containing compound, and a silicon-containing substance.

(Polymer having polyethyleneimine skeleton)

The polyethyleneimine moiety of the polymer having a polyethyleneimine skeleton may be either linear polyethyleneimine or branched polyethyleneimine, and is preferably linear polyethyleneimine.

The polymer having a polyethyleneimine skeleton may be a homopolymer of polyethyleneimine or a copolymer having a polyethyleneimine skeleton and a repeating unit other than polyethyleneimine.

When the polymer having a polyethyleneimine skeleton is a homopolymer of polyethyleneimine, the structure of the homopolymer of polyethyleneimine is not particularly limited, and may be any of a linear structure, a star-like structure, and a comb-like structure, for example.

When the polymer having a polyethyleneimine skeleton is a copolymer having a polyethyleneimine skeleton and a repeating unit other than polyethyleneimine, the proportion of the polyethyleneimine skeleton in the copolymer is preferably 20 mol% or more.

The copolymer having a polyethyleneimine skeleton and a repeating unit other than polyethyleneimine is preferably a block copolymer having a polyethyleneimine skeleton with a repeating unit number of 10 or more.

Examples of the copolymer having a polyethyleneimine skeleton and other repeating units other than polyethyleneimine include polymers other than polyethyleneimine, such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, poly (N-isopropylacrylamide), polyhydroxyethylacrylate, polymethyloxazoline, polyethyloxazoline, and polypropyleneimine.

By using these other polymers, the thickness of the water-repellent layer can be easily adjusted.

In the polymer having a polyethyleneimine skeleton, the number average molecular weight of a portion corresponding to the polyethyleneimine skeleton is preferably in the range of 500 to 1,000,000. By setting the molecular weight of the portion corresponding to the polyethyleneimine skeleton within this range, a stable water repellent layer can be formed.

The polymer having a polyethyleneimine skeleton is preferably a fibrous polymer having a linear polyethyleneimine skeleton, the thickness of which is in the range of 10 to 200nm and the length of which is in the range of 50nm to 2 μm.

The polymer having a polyethyleneimine skeleton is a basic polymer and therefore has very high polarity. Therefore, the water repellent layer that slips off and contains a polymer having a polyethyleneimine skeleton can exhibit a strong interaction (adsorption force) with various substrates such as metal substrates and resin substrates.

When the polymer having a polyethyleneimine skeleton is a fibrous polymer having a linear polyethyleneimine skeleton, the long axis thereof is preferably oriented in a direction substantially perpendicular to the surface of the substrate, or a network structure is preferably formed on the substrate.

The number of the polymers having a polyethyleneimine skeleton contained in the water-repellent layer may be 1 alone or 2 or more in combination.

(silicon-containing substance)

Examples of the silicon-containing substance contained in the slip-off water-repellent layer of the present invention include an alkoxysilane compound, water glass, ammonium hexafluorosilicate, and the like, and among these, an alkoxysilane compound is preferable.

Examples of the alkoxysilane compound include tetramethoxysilane, an oligomer of a condensate of tetramethoxysilane, tetraethoxysilane, an oligomer of a condensate of ethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, tetraethoxysilane, an oligomer of a condensate of ethoxysilane, a condensate of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, a condensate of 3-glycidoxypropyltrimethoxysilane, a condensate of a cyclic-hydroxy-containing a carboxylic acid, a compound of a cyclic amine, a derivative of a cyclic amine, and a derivative of a cyclic amine, 3-mercaptotriethoxysilane, 3,3, 3-trifluoropropyltrimethoxysilane, 3,3, 3-trifluoropropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-chloromethylphenyltrimethoxysilane, p-chloromethylphenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, etc. Among these, an oligomer of a tetramethoxysilane condensate (methyl silicate) is preferable.

The number of the silicon-containing substances contained in the water-repellent layer may be 1 or 2 or more.

(fluorine-containing Compound)

The fluorine-containing compound is not particularly limited as long as it is a compound containing a fluorine atom, and is preferably a silane compound having a perfluoroalkyl group and/or a perfluoropolyether group, and more preferably a silane compound having a fluorine atom selected from the group consisting of C_nF_2n+1Perfluoroalkyl group (n is an integer of 1 or more) and F (C) shown in the specification_nF_2nO)_mThe perfluoropolyether group (n is an integer of 1 or more, m is an integer representing the number of repetitions), and CF₃O(C_nF_2nO)_m1 or more kinds of perfluoropolyether groups (n is an integer of 1 or more, and m is an integer representing the number of repetitions) and Si (A)₃A silyl group (3A's are each independently a hydrolyzable group or a non-hydrolyzable group, and at least 1 of the 3A's is a hydrolyzable group).

Presuming that the fluorine-containing compound has Si (A)₃The silyl group is a group which can form a bond by reacting the hydrolyzable group with a hydroxyl group on the surface of the silicon-containing substance in the slip-off water-repellent layer.

C above_nF_2n+1In the perfluoroalkyl group, n is preferably 1 to 10, more preferably 1 to 6.

The aforementioned F (C)_nF_2nO)_mIn the perfluoropolyether group, n is preferably 1 to 6, more preferably 2 to 6, further preferably 1 to 3, and m is, for example, 5 on average100, preferably 8 to 80 on average, and more preferably 10 to 60 on average.

CF as described above₃O(C_nF_2nO)_mIn the perfluoropolyether group, n is preferably 1 to 6, more preferably 2 to 6, and further preferably 1 to 3, and m is, for example, 5 to 100 on average, preferably 8 to 80 on average, and more preferably 10 to 60 on average.

The fluorine-containing compound may comprise (C)_nF_2nO)_mThe perfluoropolyether chain (n is an integer of 1 or more, and m is an integer representing the number of repetitions).

Examples of the hydrolyzable group include alkoxy groups such as methoxy, ethoxy, and propoxy; alkoxy-substituted alkoxy groups such as methoxyethoxy; acyloxy groups such as acetoxy, propionyloxy, benzoyloxy and the like; alkenyloxy groups such as isopropenyloxy and isobutenyloxy; imino groups such as dimethyl ketoximino, methyl ethyl ketoximino, diethyl ketoximino and cyclohexane ketoximino; substituted amino groups such as methylamino, ethylamino, dimethylamino, and diethylamino; amide groups such as N-methylacetamide group and N-ethylamide group; substituted aminooxy groups such as dimethylaminoxy group and diethylaminooxy group; halogen such as chlorine, etc.

Among these hydrolyzable groups, alkoxy groups are preferable, alkoxy groups having 1 to 6 carbon atoms are more preferable, alkoxy groups having 1 to 3 carbon atoms are even more preferable, methoxy groups and ethoxy groups are particularly preferable, and methoxy groups are most preferable, because hydrolysis speed is high and a film having excellent durability can be formed quickly.

Examples of the non-hydrolyzable group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

Among these non-hydrolyzable groups, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable, because a steric hindrance can be avoided and the hydrolysis rate can be increased, and as a result, a coating film having excellent durability can be formed quickly.

Si(A)₃The number of hydrolyzable groups in the silyl group is at least 1, so as to formIn terms of a coating film having further excellent durability, it is preferable that all of 2 or more, more preferably 3, are hydrolyzable groups.

Note that, Si (A)₃When the number of the hydrolyzable groups in the silyl group is 2 or more, the number of the hydrolyzable groups is 2 or more, and the hydrolyzable groups may be the same or different from each other. In addition, there are more than 2 Si (A)₃In the case of the silyl group represented, at least 1 Si (A)₃The silyl group may have a hydrolyzable group. Similarly, Si (A)₃When 2 or more non-hydrolyzable groups are present in the silyl group, 2 or more non-hydrolyzable groups are optionally the same as or different from each other.

The fluorine-containing compound is preferably a compound represented by the following formula (1-1) or (1-2).

(in the above formulae (1-1) and (1-2),

rf are each independently C_nF_2n+1A perfluoroalkyl group (n is an integer of 1 or more).

The aforementioned Si (A)₃Each of 3A's of the silyl group is independently a hydrolyzable group or a non-hydrolyzable group, and at least 1 of 3A's is a hydrolyzable group.

X is any one of linking groups represented by the following formulae (X-1) to (X-11). )

(in the above formulae (X-1) to (X-11),

rf is C_nF_2n+1A perfluoroalkyl group (n is an integer of 1 or more).

R¹¹Is a direct bond or carbonAn alkylene group having 1 to 6 atoms. In the presence of a plurality of R¹¹In the case of (2), a plurality of R¹¹Optionally identical to or different from each other.

R¹²Is an alkyl group having 1 to 6 carbon atoms. )

In the formulae (1-1) and (1-2), with respect to C_nF_2n+1Perfluoroalkyl group and Si (A)₃Preferred embodiments of the silyl group are as described above.

Specific examples of the compound represented by the formula (1-1) or (1-2) include the following.

The method for producing the compound represented by the formula (1-1) or (1-2) is not particularly limited, and the compound can be produced by a known method, for example, a method disclosed in international publication No. WO 2015/152265.

The fluorine-containing compound is preferably a compound represented by the following formula (2-1), (2-2), (2-3) or (2-4).

(in the above formulae (2-1), (2-2), (2-3) and (2-4),

r is an integer representing the number of repeats.

R²¹Is an alkylene group having 1 to 6 carbon atoms.

R²³Is a linking group having a valence of 2.

Z is a linking group having a valence of 3.

Each B is independently an organic group or-Si (A)₃At least 1 of the 2 silyl groups is Si (A)₃Silyl groups as shown.

The aforementioned Si (A)₃Each of 3A's of the silyl group is independently a hydrolyzable group or a non-hydrolyzable group, and at least 1 of 3A's is a hydrolyzable group. )

In the formulae (2-1), (2-2), (2-3) and (2-4), the number of repetitions of r is preferably 5 to 100 on average, more preferably 8 to 80 on average, and still more preferably 10 to 60 on average.

In the formulae (2-1), (2-2), (2-3) and (2-4), as R²¹The alkylene group having 1 to 6 carbon atoms in (b) is preferably an alkylene group having 3 carbon atoms.

With respect to Si (A) in the formulae (2-1), (2-2), (2-3) and (2-4)₃Preferred modes of the silyl group are as described above.

When B is an organic group in the formulae (2-1) and (2-2), examples of the organic group include a substituted or unsubstituted alkyl group, an alkenyl group, and a phenyl group.

When the organic group of B is a substituted alkyl group, examples of the substituted alkyl group include a partially fluorinated alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms, and the like.

In the formulae (2-1), (2-2), (2-3) and (2-4), as R²³The linking group having a valence of 2 in (1) is preferably a linking group represented by the following formula (R-1) or a linking group represented by the following formula (R-2).

(in the above formulae (R-1) and (R-2),

R²⁴is an alkylene group having 1 to 3 carbon atoms.

R²⁵Is a direct bond or an alkylene group having 1 to 6 carbon atoms.

R²⁶Is an alkylene group having 1 to 5 carbon atoms)

Specific examples of the linking group represented by the formula (R-1) include the following.

Specific examples of the linking group represented by the formula (R-2) include the following.

As the linking group represented by the formulae (R-1) and (R-2), preferred are linking groups represented by the formulae (R-1-1), (R-1-3), (R-1-4), (R-2-5), (R-2-6) and (R-2-8), and more preferred are linking groups represented by the formulae (R-1-3) and (R-1-4).

The linking group having a valence of 3 of Z in the formulae (2-2) and (2-4) is preferably a cyclic aliphatic group having a valence of 3 and having 4 to 8 carbon atoms, and more preferably a cyclohexyl group having a valence of 3.

Specific examples of the compound represented by the formula (2-1), (2-2), (2-3) or (2-4) include the following.

(in the formulae (2-1-11) and (2-1-12), a is an integer of 1 to 6.)

The method for producing the compound represented by the formula (2-1), (2-2), (2-3) or (2-4) is not particularly limited, and the compound can be produced by a known method.

One embodiment of the method for producing the compound represented by formula (2-1), (2-2), (2-3), or (2-4) will be described below.

The method for producing the compound represented by the formulae (2-1) and (2-2) includes, for example: a step 1 of reacting a carboxylic acid represented by the following formula (. beta. -1) with an epoxysilane compound represented by the following formula (. beta. -2) or ((. beta. -3) to prepare a reactant having a secondary hydroxyl group derived from an epoxy group; and a 2 nd step of reacting the reactant obtained in the 1 st step with an isocyanate compound represented by the following formula (. beta. -4).

(in the formula (. beta. -1), r is a repetition number.)

(in the formulae (. beta. -2) and (. beta. -3),

R²³is a linking group having a valence of 2.

Si(A)₃Each of 3A's of the silyl group is independently a hydrolyzable group or a non-hydrolyzable group, and at least 1 of 3A's is a hydrolyzable group. )

(in the above formula (. beta. -4),

R²¹is an alkylene group having 1 to 6 carbon atoms.

Instead of the compound represented by the formula (. beta. -2), a compound represented by the following formula (. beta. -5) may be used.

(in the above formula (. beta. -5),

R²³is a linking group having a valence of 2.

G is an organic group. )

When the compounds represented by the formulae (2-3) and (2-4) are produced, the step 1 may be included, and the step 2 may be omitted.

Specific examples of the compound represented by the formula (. beta. -2) include the following.

Specific examples of the compound represented by the formula (. beta. -3) include the following.

Specific examples of the compound represented by the formula (. beta. -4) include the following.

(in the formula, R²¹Is an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, more preferably n-propylene group)

Specific examples of the compound represented by the formula (. beta. -5) include the following.

(a is an integer of 1-6.)

The process for producing the compound represented by the formula (2-1), (2-2), (2-3) or (2-4) may be carried out in the presence of an organic solvent, if necessary.

The organic solvent is not particularly limited as long as the compound group as a raw material can be dissolved therein, and for example, a solvent such as acetone, methyl ethyl ketone, toluene, xylene, or a fluorine-based organic solvent which is not reactive with an isocyanate group can be used.

The fluorine-containing solvent is preferably a fluorine-containing aromatic hydrocarbon solvent such as 1, 3-bis (trifluoromethyl) benzene or trifluorotoluene; perfluorocarbon solvents having 3 to 12 carbon atoms such as perfluorohexane and perfluoromethylcyclohexane; hydrofluorocarbon solvents such as 1,1,2,2,3,3, 4-heptafluorocyclopentane and 1,1,1,2,2,3,3,4,4,5,5,6, 6-tridecafluorooctane; c₃F₇OCH₃、C₄F₉OCH₃、C₄F₉OC₂H₅，C₂F₅CF(OCH₃)C₃F₇Hydrofluoroether solvents such as; perfluoropolyether compounds such as FOMBLIN, Galden (manufactured by Solvay Co., Ltd.), DEMNUM (manufactured by DAIKIN INDUSTRIES, Ltd.), and Krytox (manufactured by Chemours Co., Ltd.).

In the step 1, the ratio of the equivalent ratio (carboxyl group/epoxy group) of the carboxyl group of the compound (. beta. -1) to the epoxy group of the compound (. beta. -2) or the compound (. beta. -3) is preferably 0.5 to 1.5, more preferably 0.9 to 1.1, and still more preferably 0.98 to 1.02, with respect to the ratio of the reaction of the compound (. beta. -1) with the compound (. beta. -2) or the compound (. beta. -3).

The reaction temperature in the first step 1 is not particularly limited, but is usually 50 to 150 ℃. The reaction time is also not particularly limited, and is usually 1 to 10 hours.

In the 2 nd step, the reaction ratio of the product having a secondary hydroxyl group derived from an epoxy group obtained in the 1 st step to the compound (β -4) is preferably a ratio in which the equivalent ratio (hydroxyl group/isocyanate group) of the hydroxyl group of the reactant to the isocyanate group of the compound (β -4) is 0.5 to 1.5, more preferably 0.9 to 1.1, and still more preferably 0.98 to 1.02.

The reaction temperature in the 2 nd step is not particularly limited, but is usually 30 to 120 ℃. The reaction time is also not particularly limited, and is usually 1 to 10 hours.

The fluorine-containing compound is preferably a compound represented by the following formula (3).

(in the above-mentioned formula (3),

PFPE is a poly (perfluoroalkylene ether) chain.

Y¹And Y²Each independently is a direct bond or a 2-valent linking group.

Z¹And Z²Each independently is a 2-valent linking group.

The compound represented by formula (3) has a urethane bond in the skeleton. By having such a urethane, the polarity in the vicinity of the hydrolyzable groups at both ends is improved, and the reactivity with the silicon-containing substance is improved.

In the formula (3), with respect to Si (A)₃Preferred modes of the silyl group are as described above.

In the formula (3), as Y¹、Y²、Z¹And Z²Examples of the linking group having a valence of 2 in (c) include an alkylene group having 1 to 22 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a n-propylene group, an isopropylene group, a butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a 2, 2-dimethylpropylene group, a 2-methylbutylene group, a 2-methyl-2-butylene group, a 3-methylbutylene group, a 3-methyl-2-butylene group, a pentylene group, a 2-pentylene group, a 3-dimethyl-2-butylene group, a 3, 3-dimethylbutylene group, a 3, 3-dimethyl-2-butylene group, a 2-ethylbutylene group, a hexylene group, a 2-hexylene group, a 3-hexylene group, a 2-methylpentylene group, a 2-methyl-2-pentylene group, a 2-methyl-3-pentylene group, a, 3-Methylpentylene, 3-methyl-2-pentylene, 3-methyl-3-pentylene, 4-methylpentylene, 4-methyl-2-pentylene, 2-dimethyl-3-pentylene, 2, 3-dimethyl-3-pentylene, 2, 4-dimethyl-3-pentylene, 4-dimethyl-2-pentylene, 3-ethyl-3-pentylene, heptylene, 2-heptylene, 3-heptylene, 2-methyl-2-hexylene, 2-methyl-3-hexylene, 5-methylhexylene, 5-methyl-2-hexylene, 2-ethylhexyl, 6-methyl-2-heptylene, 2-methylpentylene, 3-methyl-3-pentylene, 4-methylpentylene, 2-methylpentylene, 3-methylpentylene, 2-hexylene, 6-methyl-2-heptylylene, 2-heptylene, 2-pentylene, 2-methylpentylene, 2-pentylene, 2-methylpentylene, 4-methylpentylene, 3-pentylene, 2-heptylene, 2-hexylene, 2-hexylene, 2, or the same, 2-hexylene, or the same, Alkylene groups such as 4-methyl-3-heptylene, octylene, 2-octylene, 3-octylene, 2-propylpentylene, 2,4, 4-trimethylpentylene, and decylene.

Z of formula (3)¹And Z²The 2-valent linking groups in (A) are each independently preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, still more preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably an n-propylene group.

Y of formula (3)¹And Y²The 2-valent linking groups in (A) are each independently preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and further preferably a methylene group.

The PFPE (poly (perfluoroalkylene ether) chain) of the formula (3) includes, for example, a linking group having a structure in which a perfluoroalkylene group having 1 to 3 carbon atoms and an oxygen atom are alternately linked.

Examples of the linking group having a structure in which a perfluoroalkylene group having 1 to 3 carbon atoms and an oxygen atom are alternately linked include a linking group represented by the following formula (P-1).

(in the above formula (P-1),

is an atomic bond.

X is a perfluoroalkylene group.

The perfluoroalkylene groups of the plurality of xs are optionally the same as or different from each other. In the plural X, 2 or more kinds of perfluoroalkylene groups may be present randomly or in a block form.

n is the number of repetitions. n is, for example, 6 to 300, preferably 12 to 200, more preferably 20 to 150, further preferably 30 to 100, most preferably 35 to 70. )

Examples of the perfluoroalkylene group as X include the following structures.

Among these, X is preferably a perfluoromethylene group (a) and a perfluoroethylene group (b), and more preferably a perfluoromethylene group (a) and a perfluoroethylene group (b) coexist, including those which are easily obtained from a process.

When the perfluoromethylene group (a) and the perfluoroethylene group (b) are present together, the presence ratio (a/b) (ratio of the number of the units) is preferably 1/10 to 10/1, more preferably 3/10 to 10/3.

Specific examples of the compound represented by the formula (3) include the following.

In the compound represented by the formula (3), the total number of fluorine atoms contained in 1 poly (perfluoroalkylene ether) chain is preferably in the range of 30 to 600, more preferably 60 to 450, further preferably 90 to 300, and most preferably 100 to 200.

The method for producing the compound represented by formula (3) is not particularly limited, and the compound can be produced by a known method. An embodiment of the method for producing the compound represented by formula (3) will be described below.

The compound represented by the formula (3) can be produced by reacting a diol represented by the following formula (. alpha. -1) with an isocyanate represented by the following formula (. alpha. -2).

(in the formulae (. alpha. -1) and (. alpha. -2) described above,

PFPE is a poly (perfluoroalkylene ether) chain.

Y¹And Y²Each independently is a direct bond or a 2-valent linking group.

Z is a linking group having a valence of 2.

PFPE, Y in the formulae (. alpha. -1) and (. alpha. -2)¹、Y²Z and Si (A)₃Respectively with PFPE, Y of formula (3)¹、Y²、Z¹And Z²And Si (A)₃And (7) corresponding.

Examples of the diol represented by the formula (. alpha. -1) include a diol represented by the following formula (. alpha. -1-1) and a diol represented by the following formula (. alpha. -1-2).

Examples of the isocyanate represented by the formula (. alpha. -2) include isocyanates represented by the following formulae (. alpha. -2-1) to (. alpha. -2-12).

Z in the isocyanate compounds represented by the formulae (α -2-1) to (α -2-12) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, still more preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably an n-propylene group.

In the reaction (carbamation) of the diol represented by the formula (. alpha. -1) with the isocyanate represented by the formula (. alpha. -2), the isocyanate represented by the formula (. alpha. -2) is preferably added in an amount of 0.5 to 1.5 mol, more preferably 0.9 to 1.1 mol, and most preferably 0.98 to 1.02 mol, based on 1 mol of OH groups contained in the diol represented by the formula (. alpha. -1).

In order to accelerate the urethanization reaction, when the diol represented by the formula (. alpha. -1) is reacted with the isocyanate represented by the formula (. alpha. -2), for example, tertiary amines such as triethylamine and benzyldimethylamine, and tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, and tin 2-ethylhexanoate may be added as catalysts.

The amount of the catalyst added is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 1.0% by mass, and still more preferably 0.02 to 0.2% by mass, based on the whole reaction mixture. The reaction time is preferably 1 to 10 hours.

In the reaction of the diol represented by the formula (. alpha. -1) with the isocyanate represented by the formula (. alpha. -2), the reaction system may be a solvent-free system or an organic solvent such as acetone, methyl ethyl ketone, toluene, xylene, etc., which does not have reactivity with the isocyanate group; c is to be₄F₉C₂H₅、(CF₃)₂CFCHFCHFCF₃、C₆F₁₃H、C₆F₁₃C₂H₅、C₄F₉OCH₃、C₄F₉OC₂H₅、C₂F₅CF(OCH₃)C₃F₇、HCF₂CF₂OCH₂CF₃And a solvent system in which a fluorine-based solvent is used as a reaction solvent.

The reaction temperature is preferably 30 to 120 ℃, and more preferably 40 to 90 ℃.

The fluorine-containing compound is preferably a compound represented by the following formula (4-1), (4-2) or (4-3).

(in the above formulae (4-1), (4-2) and (4-3),

r is an integer representing the number of repeats.

R⁴¹Is an alkylene group having 1 to 6 carbon atoms.

R⁴²Is an alkyleneaminoalkylene or alkylenethioalkylene.

With respect to the formulae (4-1), (4-2) and(4-3) the number of repetitions of r, and Si (A)₃Preferred embodiments of the silyl group are as described above.

In the formulae (4-1), (4-2) and (4-3), as R⁴¹The alkylene group having 1 to 6 carbon atoms in (b) is preferably an alkylene group having 3 carbon atoms.

In the formulae (4-1), (4-2) and (4-3), R⁴²The alkyleneaminoalkylene group in (1) is a group in which 2 alkylene groups are bonded to each other via an amino bond (-NH-), and the alkylenethioalkylene group is a group in which 2 alkylene groups are bonded to each other via a sulfur bond (-S-). Here, the alkylene group of the alkyleneaminoalkylene group and the alkylenethioalkylene group is preferably an alkylene group having 1 to 6 carbon atoms, independently of each other.

Specific examples of the compound represented by the formula (4-1), (4-2) or (4-3) include the following.

The compound represented by the formula (4-1), (4-2) or (4-3) can be produced by the same method as the method for producing the compound represented by the formula (2-1), (2-2), (2-3) or (2-4).

For example, the compound represented by the formula (4-1), (4-2) or (4-3) can be produced by reacting an alcohol represented by the following formula (. gamma. -1) with an isocyanate compound represented by the above formula (. beta. -4).

As the reaction conditions, other raw materials, and the like, the same reaction conditions and other raw materials as those of the production method of the compound represented by the formula (2-1), (2-2), (2-3), or (2-4) can be employed.

(in the formula (. gamma. -1), r is a repetition number.)

The fluorine-containing compound is preferably a compound represented by the following formula (5-1), (5-2) or (5-3).

(in the above formulae (5-1), (5-2) and (5-3),

l is an integer representing the number of repetitions.

m is an integer representing the number of repetitions.

R⁵¹Is an alkylene group having 1 to 6 carbon atoms.

R⁵²Is an alkyleneaminoalkylene or alkylenethioalkylene.

In the formulae (5-1), (5-2) and (5-3), the number of repetitions of l and m, and Si (A)₃Preferred embodiments of the silyl group are as described above.

In the formulae (5-1), (5-2) and (5-3), as R⁵¹The alkylene group having 1 to 6 carbon atoms in (b) is preferably an alkylene group having 3 carbon atoms.

In the formulae (5-1), (5-2) and (5-3), R⁵²The alkyleneaminoalkylene group in (1) is a group in which 2 alkylene groups are bonded to each other via an amino bond (-NH-), and the alkylenethioalkylene group is a group in which 2 alkylene groups are bonded to each other via a sulfur bond (-S-). Here, the alkylene group of the alkyleneaminoalkylene group and the alkylenethioalkylene group is preferably an alkylene group having 1 to 6 carbon atoms, independently of each other.

Specific examples of the compound represented by the formula (5-1), (5-2) or (5-3) include the following.

The same method as that for the production of the compound represented by the formula (4-1), (4-2) or (4-3) can be employed for the production of the compound represented by the formula (5-1), (5-2) or (5-3).

For example, the compound represented by the formula (5-1), (5-2) or (5-3) can be produced by using an alcohol represented by the following formula (δ -1) in place of the alcohol represented by the above formula (γ -1).

(in the above formula (. delta. -1),

l is the number of repetitions.

m is the number of repetitions. )

The number of the fluorine-containing compounds in the water-repellent layer may be 1 or more than 2.

(other Components)

The water-repellent layer may contain other components as long as it contains a polymer having a polyethyleneimine skeleton, a fluorine-containing compound and a silicon-containing substance, and the effects of the present invention are not impaired.

The slip water-repellent layer may contain or may not contain other components in addition to the polymer having a polyethyleneimine skeleton, the fluorine-containing compound, and the silicon-containing substance.

The slip water-repellent layer is preferably substantially formed of a polymer having a polyethyleneimine skeleton, a fluorine-containing compound and a silicon-containing substance, and in this case, the slip water-repellent layer may contain inevitable impurities.

In the polymer having a polyethyleneimine skeleton, the fluorine-containing compound and the silicon-containing substance in the slip water-repellent layer, it is preferable that the polymer having a polyethyleneimine skeleton is covered with the silicon-containing substance to form a polyethyleneimine-silicon-containing substance composite in which the fluorine-containing compound is bonded to the silicon-containing substance.

When the polymer having a polyethyleneimine skeleton in the polyethyleneimine-silicon-containing substance composite is the aforementioned fibrous polymer having a linear polyethyleneimine skeleton, and the long axis thereof is oriented in a direction substantially perpendicular to the surface of the base material, the fibrous composite having a nanoscale size covers the surface of the base material in a turf-like manner (this state is sometimes referred to as "nanogrid").

When the polymer having a polyethyleneimine skeleton in the polyethyleneimine-silicon-containing substance composite is a fibrous polymer having a linear polyethyleneimine skeleton as described above and a network structure is formed on the substrate, the surface of the substrate is covered with a nano-scale network structure (this state is sometimes referred to as "nanosponging").

It is presumed that when the polyethyleneimine-silicon-containing substance complex on the surface of the substrate is a nanogrid or a nanosponge, the surface of the sliding water-repellent layer is a fine uneven structure, and the water-repellent effect and the water-sliding effect of the structure of the present invention are improved.

A structure according to still another embodiment of the present invention is a structure having a slip-off water-repellent layer containing a fluorine-containing compound and a silicon-containing substance on a substrate, and the silicon-containing substance in the slip-off water-repellent layer has a nano-turf shape or a nano-sponge shape.

By the production method described later, only polyethyleneimine can be removed from the polyethyleneimine-silicon-containing substance complex contained in the slip water-repellent layer to form a silicon-containing substance in the form of a nanogrid or a nanosponge.

The structure of the present embodiment is the same as the structure of the above embodiment except that the slip-off water-repellent layer does not contain a polymer having a polyethyleneimine skeleton, and preferred embodiments of the substrate, the fluorine-containing compound, the silicon-containing substance, and the like are the same as those of the substrate, the fluorine-containing compound, the silicon-containing substance, and the like.

< method for producing Structure >

The method for producing a structure of the present invention includes the following steps (1), (2), and (3):

a step (1) of bringing a substrate into contact with a solution containing a polymer having a polyethyleneimine skeleton to form a layer containing the polymer having a polyethyleneimine skeleton on the surface of the substrate

A step (2) of bringing a laminate comprising the substrate and the layer comprising the polymer having a polyethyleneimine skeleton into contact with a silicon-containing substance source liquid to form a silicon-containing substance in the layer comprising the polymer having a polyethyleneimine skeleton

A step (3) of treating the layer containing the polymer having a polyethyleneimine skeleton, on which the silicon-containing substance has been formed, with a fluorine-containing compound

In the step (1), the polymer having a polyethyleneimine skeleton is the same as the polymer having a polyethyleneimine skeleton contained in the water-repellent layer for slipping down of the structure of the present invention, and the base material is the same as the base material of the structure of the present invention.

The solvent used for preparing the solution of the polymer having a polyethyleneimine skeleton is not particularly limited as long as it is a solvent capable of dissolving the polymer having a polyethyleneimine skeleton, and an organic solvent such as methanol or ethanol, water, or a mixed solvent thereof may be used.

The concentration of the polymer having a polyethyleneimine skeleton in the solution containing the polymer having a polyethyleneimine skeleton is, for example, 0.5 to 50% by mass, preferably 1.0 to 20% by mass, and more preferably 1.0 to 10% by mass.

The solution of the polymer having a polyethyleneimine skeleton may or may not contain a polymer other than the polymer having a polyethyleneimine skeleton.

The aforementioned other polymer is preferably compatible with the aforementioned polymer having a polyethyleneimine skeleton.

The concentration of the aforementioned other polymers can be set as appropriate.

The contact between the base material and the solution containing the polymer having a polyethyleneimine skeleton is not particularly limited, and may be performed by immersing the base material in the solution containing the polymer having a polyethyleneimine skeleton, applying the solution containing the polymer having a polyethyleneimine skeleton to the base material, or the like, and preferably immersing the base material in the solution containing the polymer having a polyethyleneimine skeleton.

In the case where the base material is immersed in the solution containing the polymer having a polyethyleneimine skeleton, the base material is preferably immersed in a cleaning solution and cleaned before immersion.

Examples of the cleaning liquid include organic solvents such as acetone, methyl ethyl ketone, and toluene, water, ethanol, isopropanol, an aqueous sodium hydroxide solution, an aqueous tetramethylammonium hydroxide solution, and a mixture thereof.

By cleaning the substrate with the cleaning liquid in advance, stains such as oil on the surface of the substrate can be removed, and the layer containing the polymer having a polyethyleneimine skeleton can be formed smoothly.

When the substrate is brought into contact with the solution containing the polymer having a polyethyleneimine skeleton, the solution containing the polymer having a polyethyleneimine skeleton is preferably brought to a temperature higher than room temperature, and preferably 50 to 90 ℃.

The contact time is not particularly limited, and may be suitably set within a range of several seconds to 1 hour depending on the material and size of the substrate. For example, when the substrate is a metal substrate, the contact time is preferably several seconds to several minutes, and when the substrate is a resin substrate, the contact time is preferably several tens of minutes to 1 hour.

After the substrate is brought into contact with the solution containing the polymer having a polyethyleneimine skeleton, the contacted substrate is left at room temperature (about 25 ℃), whereby the crystallization of the polymer having a polyethyleneimine skeleton progresses, and an aggregate (a nanogrid or a nanosponge) of the polymer having a polyethyleneimine skeleton can be formed on the surface of the substrate.

The aggregate (nano turf or nano sponge) of the polymer having a polyethyleneimine skeleton can be formed on the surface of the base material by contacting the base material with a solution containing the polymer having a polyethyleneimine skeleton, and then contacting the base material with water at 4 to 30 ℃ or an aqueous ammonia solution at a temperature of room temperature to below the freezing point.

In the step (2), the silicon-containing substance source liquid is a solution of a silicon-containing substance contained in the slip water-repellent layer of the structure of the present invention, and is preferably a solution of an alkoxysilane compound.

Examples of the silicon-containing material source liquid include an aqueous solution of a silicon-containing material, an alcohol solution of a silicon-containing material, and a mixed solvent solution of water and alcohol of a silicon-containing material. Examples of the alcohol include methanol, ethanol, and propanol. The concentration of the silicon-containing substance in the silicon-containing substance source liquid is, for example, 0.5 to 50% by mass, preferably 1.0 to 20% by mass, and more preferably 1.0 to 10% by mass.

As the silicon-containing source liquid, a water glass aqueous solution having a pH adjusted to a range of 9 to 11 may be used. In the case where the silicon-containing substance is an alkoxysilane compound, a bulk liquid of the alkoxysilane compound without a solvent may be used as the silicon-containing substance source liquid.

The contact between the laminate comprising the base material and the layer containing a polymer having a polyethyleneimine skeleton and the silicon-containing substance source liquid is not particularly limited, and the contact may be performed by immersing the laminate in the silicon-containing substance source liquid, applying the silicon-containing substance source liquid to the layer containing a polymer having a polyethyleneimine skeleton of the laminate, or the like, and preferably immersing the laminate in the silicon-containing substance source liquid.

When the laminate including the base material and the layer containing the polymer having a polyethyleneimine skeleton is brought into contact with the silicon-containing substance source liquid, the temperature of the silicon-containing substance source liquid may be room temperature, or may be higher than room temperature by heating. When the silicon-containing substance source liquid is set to a temperature higher than room temperature, it is preferably set to 70 ℃ or lower in order to form a silicon-containing substance regularly.

The contact time is not particularly limited, and may be suitably set according to the size of the laminate, and is, for example, 5 to 60 minutes.

The silicon-containing substance can be produced by bringing a laminate comprising a base material and a layer containing a polymer having a polyethyleneimine skeleton into contact with a silicon-containing substance source liquid, whereby the silicon-containing substance source is hydrolytically condensed on the surface of the polymer having a polyethyleneimine skeleton. This enables formation of a silicon-containing substance that covers a part or all of the surface of the polymer having a polyethyleneimine skeleton.

The laminate comprising a base material and a layer containing a polymer having a polyethyleneimine skeleton is allowed to stand at room temperature for a few minutes after being brought into contact with a silicon-containing substance source liquid, and then dried at 40 to 200 ℃ for 5 to 60 minutes, whereby a silicon-containing substance covering a part or all of the polymer having a polyethyleneimine skeleton can be formed.

The drying temperature is preferably 40-150 ℃, and the drying time is preferably 30-60 minutes.

In the step (3), the fluorine-containing compound is the same as the fluorine compound contained in the water-repellent layer of the structure of the present invention.

The fluorine-containing compound is preferably in the form of a solution obtained by dissolving the fluorine-containing compound in a solvent, for example. Examples of the solvent for the fluorine-containing compound include a fluorine-containing aromatic hydrocarbon solvent such as 1, 3-bis (trifluoromethyl) benzene and benzotrifluoride; perfluorocarbon solvents having 3 to 12 carbon atoms such as perfluorohexane and perfluoromethylcyclohexane; hydrofluorocarbon solvents such as 1,1,2,2,3,3, 4-heptafluorocyclopentane and 1,1,1,2,2,3,3,4,4,5,5,6, 6-tridecafluorooctane; c₃F₇OCH₃、C₄F₉OCH₃、C₄F₉OC₂H₅、C₂F₅CF(OCH₃)C₃F₇Hydrofluoroether solvents such as; perfluoropolyether compounds such as FOMBLIN, Galden (manufactured by Solvay), DEMNUM (manufactured by DAIKIN INDUSTRIES, Ltd.), and Krytox (manufactured by Chemours).

The concentration of the fluorine-containing compound in the solution obtained by dissolving the fluorine-containing compound in the solvent is, for example, 0.01 to 10% by mass, preferably 0.1 to 5% by mass.

The treatment with the fluorine-containing compound to form the layer containing the polymer having a polyethyleneimine skeleton containing a silicon-containing substance is, for example, contact of a laminate comprising a substrate and a layer containing the silicon-containing substance and the polymer having a polyethyleneimine skeleton with the fluorine-containing compound.

The contact between the laminate comprising the substrate and the layer containing the silicon-containing substance and the polymer having a polyethyleneimine skeleton and the fluorine-containing compound is not particularly limited, and may be performed by immersing the laminate in a fluorine-containing compound solution, applying a fluorine-containing compound solution to the layer containing the silicon-containing substance and the polymer having a polyethyleneimine skeleton of the laminate, or the like, and preferably immersing the laminate in a fluorine-containing compound solution.

After the laminate is brought into contact with the fluorine-containing compound, the laminate is allowed to stand at room temperature for several minutes, and then dried at 40 to 200 ℃ for 5 to 60 minutes, whereby the fluorine-containing compound can be efficiently bonded to the resultant silicon-containing substance.

Another embodiment of the method for manufacturing a structure of the present invention includes the following steps (1), (2), (4), and (5):

A step (4) of removing the polymer having a polyethyleneimine skeleton by baking a laminate comprising the substrate and a layer comprising the polymer having a polyethyleneimine skeleton and the silicon-containing substance (step (4))

A step (5) of treating the layer containing a silicon-containing substance from which the polymer having a polyethyleneimine skeleton has been removed with a fluorine-containing compound

In another embodiment, a method for producing a structure according to the present invention includes bringing a laminate including a base material and a layer containing a polymer having a polyethyleneimine skeleton into contact with a silicon-containing substance source liquid to form a silicon-containing substance covering a part or all of the polymer having the polyethyleneimine skeleton, and then firing the silicon-containing substance to remove the polymer having the polyethyleneimine skeleton.

The polymer having a polyethyleneimine skeleton is removed by baking, but the resulting silicon-containing substance can maintain the shape of the polymer having a polyethyleneimine skeleton. For example, when the polymer having a polyethyleneimine skeleton is formed into a nanogrid, a nanogrid formed of a silicon-containing substance can be formed, and when the polymer having a polyethyleneimine skeleton is formed into a nanogap, a nanogap formed of a silicon-containing substance can be formed.

The conditions for firing the laminate comprising the base material and the layer containing the polymer having a polyethyleneimine skeleton and the silicon-containing substance may be, for example, such that the firing temperature is in the range of 300 to 600 ℃ and the firing time is in the range of 1 to 7 hours.

In the step (5) of the method for producing a structure according to the present invention, the treatment with a fluorine-containing compound may be the same as in the step (3).

< Member for Heat exchanger >

In the structure of the present invention, the water slip angle at which water slips off the surface of the water-repellent layer is preferably 5 ° or less. In the structure of the present invention, the contact angle of water on the surface of the slip water-repellent layer is preferably 160 ° or more. The sliding angle and the contact angle were evaluated by the methods described in examples.

In the structure of the present invention, the slip water-repellent layer is a layer containing a polymer having a polyethyleneimine skeleton, a silicon-containing substance, and a fluorine-containing compound, or the slip water-repellent layer is a layer containing a silicon-containing substance and a fluorine-containing compound in a nano turf shape or a nano sponge shape, and both of excellent water repellency and excellent water slipping property can be exhibited. Therefore, by using the structure of the present invention as a member for a heat exchanger, adhesion of dew condensation water and/or frost to the surface of the base material can be suppressed, and high heat exchange efficiency can be achieved.

The heat exchanger 1 of fig. 3 includes a plurality of fins 2 arranged in parallel with gaps therebetween, and a heat transfer tube 4 attached to the plurality of fins 2. The heat exchanger 1 has the fins 2 corresponding to the structure of the present invention.

The fins 2 are flat plate members for increasing the heat transfer area in the heat exchanger 1, and a plurality of fins 2 are arranged substantially in parallel with each other with a certain gap therebetween. The heat transfer pipe 4 is a cylindrical pipe in which the cooling medium flows, and has one end 6 and the other end 7. The heat transfer tubes 4 are bent a predetermined number of times and arranged to penetrate the fins 2a plurality of times.

During operation of the apparatus including heat exchanger 1, the cooling medium flows into heat transfer pipe 4 from one end 6, and air is sent to heat exchanger 1. Next, heat exchange between the air and the cooling medium is performed in the heat exchanger 1, and the cooling medium flows out from the other end 7.

The heat exchanger 1 using the structure of the present invention can repel water and slide down the surface of the fin 2 even if water droplets are generated due to dew condensation when the temperature of the surface of the fin 2 is at the dew point or lower during operation. This also suppresses the frost on the surface of the heat sink 2.

In the heat exchanger 1, a plurality of fins 2 are arranged in parallel so that their main surfaces face each other. Here, the distance of the gap between the main surfaces of the plurality of fins 2 is preferably 0.5mm or more and 3.0mm or less, more preferably 1.0mm or more and 2.0mm or less, and further preferably 1.5mm or more and 2.0mm or less.

The heat exchanger of the present invention may be of any type, such as cross fin, microchannel, etc.

The heat exchanger of the present invention can be used for, for example, air conditioners, coolers (refrigerators and freezers), electric vehicles, and the like.

Examples

The present invention will be specifically described below with reference to examples and comparative examples. The present invention is not limited to the following examples.

Synthesis example 1

< Synthesis of Linear polyethyleneimine (L-PEI) >

Commercially available polyethyloxazoline (number average molecular weight: 50,000, average degree of polymerization: 5,000, manufactured by Aldrich) was dissolved in 3g of 3 mL of 5 mol/L hydrochloric acid. The solution was heated to 90 ℃ in an oil bath and stirred at this temperature for 10 hours. To the reaction solution, 50mL of acetone was added to completely precipitate the polymer, and the obtained precipitate was filtered and washed with methanol 3 times to obtain white polyethyleneimine powder.

By using¹H-NThe obtained powder was identified by MR (heavy water, AL300, 300MHz manufactured by Nippon electronics Co., Ltd.), and it was confirmed that the peak of side chain ethyl group derived from polyethyloxazoline was 1.2ppm (CH)₃) And 2.3ppm (CH)₂) Completely disappear. That is, it was shown that polyethyloxazoline was completely hydrolyzed and converted to polyethyleneimine.

This powder was dissolved in 5mL of distilled water, and 50mL of 15% aqueous ammonia was added dropwise while stirring the solution. The resulting mixed solution was placed at night, the precipitated polymer association powder was filtered, and the filtered polymer association powder was washed with cold water 3 times. The washed crystal powder was dried at room temperature in a dryer to obtain linear polyethyleneimine (L-PEI).

The yield of linear polyethylenimine was 2.2g (containing water of crystallization). The polyethyleneimine obtained by hydrolysis of polyoxazoline reacts only on the side chain, leaving no change in the main chain. Therefore, the degree of polymerization of L-PEI was the same as that of 5,000 before hydrolysis.

Synthesis example 2

< Synthesis of silane Compound having perfluoropolyether group >

60.62g of 1, 3-bis (trifluoromethyl) benzene as a solvent, 87.6g of a carboxylic acid represented by the following formula (Krytox 157FS (H) manufactured by Chemours) and 3.33g of gamma-glycidoxypropyltrimethoxysilane were charged into a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device, and 0.273g of triphenylphosphine as a reaction catalyst were stirred under a nitrogen stream, heated to 105 ℃ and reacted for about 5 hours.

(r is the number of repeats, averaging 43.)

After the reaction, the temperature was lowered to 50 ℃ and hydrofluoroether (C) was added as a solvent to the reaction solution₄F₉OC₂H₅)33.33g of 3-isocyanatopropyltrimethoxysilane, 3.02g of 3-isocyanatopropyltrimethoxysilane and 0.047g of tin octylate as a carbamation catalyst were stirred under a stream of nitrogen at 70 ℃ CThe reaction was carried out for about 4 hours to obtain the following compound (1a) as a silane compound having a perfluoropolyether group.

(wherein r is the number of repeats, and the average is 43.)

Hydrofluoroether (C) was used so that the concentration of the solvent became 80 mass%₄F₉OC₂H₅) The reaction solution was diluted. The diluted reaction solution was purified by filtration using a Polytetrafluoroethylene (PTFE) filter having a pore diameter of 1 μm to obtain a hydrofluoroether solution containing a silane compound (1a) having a poly (perfluoroalkylene ether) chain.

Synthesis example 3

Into a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device were charged 36.67g of 1, 3-bis (trifluoromethyl) benzene as a solvent, 50g of a carboxylic acid represented by the following formula (Krytox 157FS (L) manufactured by Chemours corporation), 5.01g of γ -glycidoxypropyltrimethoxysilane and 0.165g of triphenylphosphine as a reaction catalyst, and the mixture was stirred under a nitrogen stream, heated to 105 ℃ and reacted for about 5 hours.

(r is 13 on average)

After the reaction, the temperature was lowered to 50 ℃ and hydrofluoroether (C) was added as a solvent to the reaction solution₄F₉OC₂H₅)2.97g, 4.63g of 3-isocyanatopropyltrimethoxysilane and 0.018g of tin octylate as a urethanization catalyst were added, and the mixture was stirred under a nitrogen stream and reacted at 70 ℃ for about 4 hours to obtain the following compound (2a) as a silane compound having a perfluoropolyether group.

(wherein r is the number of repeats, and the average is 13.)

Hydrofluoroether (C) was used so that the concentration of the solvent became 80 mass%₄F₉OC₂H₅) The reaction solution was diluted. The diluted reaction solution was purified by filtration using a Polytetrafluoroethylene (PTFE) filter having a pore diameter of 0.2. mu.m, to obtain a hydrofluoroether solution containing a silane compound (2a) having a poly (perfluoroalkylene ether) chain.

Synthesis example 4

40.0g of an alcohol having a poly (perfluoroalkylene ether) chain represented by the following formula and hydrofluoroether (C) as a solvent were placed in a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device₄F₉OC₂H₅)43.77g and 0.004g of tin octylate as a urethane-forming catalyst, stirring was started under a nitrogen stream. After the stirring was started, 3.77g of 3-isocyanatopropyltrimethoxysilane was added dropwise to the reaction mixture over 15 minutes while keeping the temperature at 50 ℃. After completion of the dropwise addition, the alcohol was reacted with 3-isocyanatopropyltrimethoxysilane by stirring at 50 ℃ for 6 hours to obtain a product.

(wherein r is the number of repeats, and the average is 13.)

The IR spectrum measurement of the obtained product confirmed the disappearance of the isocyanate group in the product, and the following compound (3a) was obtained.

Hydrofluoroether (C) was used so that the concentration of the solvent became 80 mass%₄F₉OC₂H₅) The reaction solution was diluted. The diluted reaction solution was purified by filtration using a Polytetrafluoroethylene (PTFE) filter having a pore diameter of 0.2. mu.m, to obtain a hydrofluoroether solution containing a silane compound (3a) having a poly (perfluoroalkylene ether) chain.

(wherein r is 13 on average.)

Synthesis example 5

Into a glass flask equipped with a stirring device, a thermometer, a condenser and a dropping device were charged 20g of an alcohol having a poly (perfluoroalkylene ether) chain represented by the following formula and hydrofluoroether (C) as a solvent₄F₉OC₂H₅)20g and 0.006g of tin octylate as a urethane-forming catalyst, 1.31g of 3-isocyanatopropyltrimethoxysilane was added dropwise over 15 minutes while maintaining 50 ℃ under stirring under a nitrogen stream.

After completion of the dropwise addition, the alcohol was reacted with 3-isocyanatopropyltrimethoxysilane by stirring at 50 ℃ for 6 hours to obtain a product.

(wherein l is the number of repeats, and m is the number of repeats, and 19 on average.)

The IR spectrum measurement of the obtained product confirmed the disappearance of the isocyanate group in the product, and the following compound (4a) was obtained.

Hydrofluoroether (C) was used so that the concentration of the solvent became 80 mass%₄F₉OC₂H₅) The reaction solution was diluted. The diluted reaction solution was purified by filtration using a Polytetrafluoroethylene (PTFE) filter having a pore diameter of 0.2. mu.m, to obtain a hydrofluoroether solution containing a silane compound (4a) having a poly (perfluoroalkylene ether) chain.

Synthesis example 6

Into a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device were charged 45.3g of a diol having a poly (perfluoroalkylene ether) chain represented by the following formula and 0.025g of tin octylate as a urethane-forming catalyst, and 4.7g of 3-isocyanatopropyltrimethoxysilane was dropped over 15 minutes while maintaining 60 ℃ under stirring under a nitrogen stream.

After the completion of the dropwise addition, the mixture was stirred at 60 ℃ for 1 hour, and then heated to 80 ℃ for 2 hours, whereby the diol and 3-isocyanatopropyltrimethoxysilane were reacted to obtain a product.

(in the formula, n is a repetition number.

Each of the plurality of xs is independently a perfluoromethylene group or a perfluoroethylene group, and the number of perfluoromethylene groups is 21 on average, the number of perfluoroethylene groups is 21 on average, and the number of fluorine atoms is 126 on average per 1 molecule of the compound. )

The IR spectrum measurement of the obtained product confirmed the disappearance of the isocyanate group in the product, and the following compound (5a) was obtained.

Hydrofluoroether (C) was used so that the concentration of the solvent became 80 mass%₄F₉OC₂H₅) The reaction solution was diluted. The diluted reaction solution was purified by filtration using a Polytetrafluoroethylene (PTFE) filter having a pore diameter of 0.2. mu.m, to obtain a hydrofluoroether solution containing a silane compound (5a) having a poly (perfluoroalkylene ether) chain.

(wherein PFPE is the same as the above- (X-O-)_n-X-corresponds. )

Synthesis example 7

50g of trifluoroethanol and hydrofluoroether (C) as a solvent were put in a glass flask equipped with a stirring device, a thermometer, a condenser and a dropping device₄F₉OC₂H₅)157.99g and 0.047g of tin octylate as a urethane-forming catalyst, and stirring was started under a nitrogen stream while keeping 5g107.99g of 3-isocyanatopropyltrimethoxysilane were added dropwise over a period of 15 minutes at 0 ℃.

When the IR spectrum measurement of the obtained product was performed, the disappearance of the isocyanate group in the product was confirmed, and it was confirmed that the perfluoroalkyl group-containing silane compound (6a) was obtained.

Hydrofluoroether (C) was used so that the concentration of the solvent became 80 mass%₄F₉OC₂H₅) The reaction solution was diluted. The diluted reaction solution was filtered and purified using a Polytetrafluoroethylene (PTFE) filter having a pore diameter of 0.2. mu.m, to obtain a hydrofluoroether solution containing a perfluoroalkyl group-containing silane compound (6 a).

Synthesis example 8

25g of 2- (perfluorohexyl) ethanol and hydrofluoroether (C) as a solvent were put into a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device₄F₉OC₂H₅)39.98g and 0.01g of tin octylate as a urethane-forming catalyst, 14.98g of 3-isocyanatopropyltrimethoxysilane was added dropwise thereto over 15 minutes while keeping the temperature at 50 ℃ under stirring under a nitrogen stream.

The IR spectrum measurement of the obtained product confirmed the disappearance of the isocyanate group in the product, and the perfluoroalkyl group-containing silane compound (7a) was confirmed to be obtained.

Hydrofluoroether (C) was used so that the concentration of the solvent became 80 mass%₄F₉OC₂H₅) The reaction solution was diluted. The diluted reaction solution was filtered and purified using a Polytetrafluoroethylene (PTFE) filter having a pore diameter of 0.2. mu.m, to obtain a hydrofluoroether solution containing the perfluoroalkyl group-containing silane compound (7 a).

Synthesis example 9

Comprises a stirring device, a thermometer, a condenser tube, and a dropping deviceInto a glass flask of (1) was charged 25g of hexafluoroisopropyl alcohol and hydrofluoroether (C) as a solvent₄F₉OC₂H₅)54.9g and 0.016g of tin octylate as a urethane-forming catalyst, 29.9g of 3-isocyanatopropyltrimethoxysilane was added dropwise thereto over 15 minutes while keeping the temperature at 50 ℃ under stirring under a nitrogen stream.

The IR spectrum measurement of the obtained product confirmed the disappearance of the isocyanate group in the product, and the result confirmed that the perfluoroalkyl group-containing silane compound (8a) was obtained.

Hydrofluoroether (C) was used so that the concentration of the solvent became 80 mass%₄F₉OC₂H₅) The reaction solution was diluted. The diluted reaction solution was filtered and purified using a Polytetrafluoroethylene (PTFE) filter having a pore diameter of 0.2. mu.m, to obtain a hydrofluoroether solution containing a perfluoroalkyl group-containing silane compound (8 a).

< production and evaluation of aluminum Flat plate having super Water repellent surface >

Example 1

An aluminum flat plate having a length of 2.5cm, a width of 7.5cm and a thickness of 0.5mm was immersed in a 0.5 mass% aqueous sodium hydroxide solution for 10 minutes, and then washed with water and methanol, respectively. Next, the flat aluminum plate was immersed in a 5 mass% L-PEI aqueous solution (80 ℃ C.) and allowed to stand for 30 seconds. The aluminum plate was taken out, allowed to stand at room temperature for 5 minutes, and then placed in a 10 mass% aqueous solution of methyl silicate, and then allowed to stand at room temperature for 30 minutes.

The aluminum plate taken out of the methyl silicate aqueous solution was dried at 150 ℃ for 30 minutes. The surface of the dried aluminum flat plate (aluminum flat plate a) was observed with a Scanning Electron Microscope (SEM), and it was confirmed that the entire surface of the aluminum flat plate a was covered with a layer (nano turf) having nanofibers of a polyethyleneimine polymer covered with a silicon-containing substance as basic units. The SEM photographs are shown in fig. 1(20000 × magnification) and fig. 2(2000 × magnification).

The observation of the surface of the aluminum flat plate by the scanning electron microscope was performed as follows: the dried flat aluminum plate was fixed to a sample holder with a double-sided adhesive tape, and observed with a surface observation device VE-9800 manufactured by KEYENCE CORPORATION.

To the hydrofluoroether solution of compound (1a) prepared in synthetic example 2 was further added hydrofluoroether to prepare a 0.1 mass% solution of compound (1 a). The aluminum plate A was immersed in a 0.1 mass% solution of the compound (1a) and allowed to stand for 1 hour. After standing, the aluminum plate was taken out and dried at 150 ℃ for 30 minutes to obtain a nano-turf aluminum plate (aluminum plate B) treated with a fluorine-containing compound.

The results of the following evaluations of the obtained aluminum flat plate B are shown in table 1.

(measurement of slip Angle)

Using a contact angle/slip angle measuring apparatus (DM-500, manufactured by Kyowa Kagaku K.K.), 5. mu.L of a water droplet of ultrapure water was dropped on the layer of the nano turf treated with a fluorine-containing compound of the aluminum flat plate B, and the mounting table was tilted at a speed of 2 degrees/sec, and the angle at which the water droplet started to move was defined as the value of the slip angle. The measurement was performed 5 times, and the average value of 5 times was defined as the slip angle of the aluminum plate B.

(contact Angle measurement)

Using a contact angle/sliding angle measuring apparatus (DM-500, manufactured by Kyowa Kagaku K.K.), 5. mu.L of a water droplet of ultrapure water was dropped on the layer of the fluorinated compound-treated nanograst of the aluminum flat plate B, and the contact angle of the water droplet was measured. The contact angle was measured 5 times, and the average value of the 5 times was defined as the contact angle of the aluminum flat plate B.

Examples 2 to 8

Aluminum flat plates C to I were produced and evaluated in the same manner as in example 1, except that compounds (2a) to (8a) were used instead of compound (1 a). The results are shown in Table 1.

Comparative example 1

The aluminum flat plate a was evaluated for the sliding angle and the contact angle in the same manner as in example 1. The results are shown in Table 1.

Comparative example 2

An aluminum flat plate J was produced and evaluated in the same manner as in example 1, except that an aluminum flat plate (an aluminum flat plate on which a nano turf was not formed) was used instead of the aluminum flat plate a. The results are shown in Table 1.

Comparative example 3

An aluminum flat plate having a length of 2.5cm, a width of 7.5cm and a thickness of 0.5mm was immersed in a 0.5 mass% aqueous sodium hydroxide solution for 10 minutes, and then washed with water and methanol, respectively. Subsequently, the aluminum flat plate was immersed in a 5 mass% triethanolamine aqueous solution at 90 ℃ for 5 minutes, and then washed with water and methanol, respectively.

To the hydrofluoroether solution of compound (1a) prepared in synthetic example 2 was further added hydrofluoroether to prepare a 0.1 mass% solution of compound (1 a). An aluminum plate treated with triethanolamine was immersed in a 0.1 mass% solution of the compound (1a) and allowed to stand for 1 hour. After standing, the aluminum plate was taken out and dried at 150 ℃ for 30 minutes to obtain an aluminum plate K.

The obtained aluminum flat plate K was evaluated in the same manner as in example 1. The results are shown in Table 1.

Comparative example 4

Butyl acetate was added to dodecyl trimethoxysilane to prepare a 0.1 mass% dodecyl trimethoxysilane solution. The aluminum plate A was immersed in the 0.1 mass% dodecyltrimethoxysilane solution and allowed to stand for 1 hour. After standing, the aluminum plate was taken out and dried at 150 ℃ for 30 minutes to obtain an aluminum plate L.

The obtained aluminum flat plate L was evaluated in the same manner as in example 1. The results are shown in Table 1.

[ Table 1]

PEI: polyethylene imine

MS: silicic acid methyl ester

TEA: triethanolamine

DMS: dodecyl trimethoxy silane

Description of the reference numerals

1. Heat exchanger

2. Heat sink

4. Heat conduction pipe

6. One end of the heat conduction pipe

7. The other end of the heat conduction pipe

Claims

1. A structure having a slip-off water-repellent layer on a substrate,

the slip water repellent layer comprises: a polymer having a polyethyleneimine skeleton, a fluorine-containing compound, and a silicon-containing substance.

2. The structure according to claim 1, wherein the polymer having a polyethyleneimine skeleton is covered with the silicon-containing substance, and the fluorine-containing compound is bonded to the silicon-containing substance.

3. The structure according to claim 1 or 2, wherein the fluorine-containing compound is a silane compound having a perfluoroalkyl group and/or a perfluoropolyether group.

4. The structure according to any one of claims 1 to 3, wherein the fluorine-containing compound is a fluorine-containing compound having a structure selected from the group consisting of C_nF_2n+1A perfluoroalkyl group represented by the formula F (C)_nF_2nO)_mThe perfluoropolyether group and CF₃O(C_nF_2nO)_m1 or more kinds of perfluoropolyether groups and Si (A)₃A silyl group represented by the formula C_nF_2n+1Wherein n is an integer of 1 or more, and F (C)_nF_2nO)_mWherein n is an integer of 1 or more, m is an integer representing the number of repetitions, and CF₃O(C_nF_2nO)_mWherein n is an integer of 1 or more, m is an integer representing the number of repetitions, and Si (A)₃In the (b), 3A's are each independently a hydrolyzable group or a non-hydrolyzable group, and at least 1 of the 3A's is a hydrolyzable group.

5. The structure according to any one of claims 1 to 3, wherein the fluorine-containing compound is a compound represented by the following formula (1-1) or (1-2),

in the formulae (1-1) and (1-2),

rf is C_nF_2n+1Wherein n is an integer of 1 or more, and when a plurality of Rf's are present, the plurality of Rf's are optionally the same as or different from each other,

said Si (A)₃Each of 3A's of the silyl group is independently a hydrolyzable group or a non-hydrolyzable group, at least 1 of 3A's is a hydrolyzable group,

x is any one of linking groups represented by the following formulae (X-1) to (X-11),

in the formulae (X-1) to (X-11),

rf is C_nF_2n+1A perfluoroalkyl group represented by (I), wherein n is an integer of 1 or more,

R¹¹a plurality of R are present in the form of direct bond or C1-6 alkylene¹¹In the case of (2), a plurality of R¹¹Optionally the same or different from each other,

R¹²is an alkyl group having 1 to 6 carbon atoms.

6. The structure according to any one of claims 1 to 3, wherein the fluorine-containing compound is a compound represented by the following formula (2-1), (2-2), (2-3) or (2-4),

in the above-mentioned formulae (2-1), (2-2), (2-3) and (2-4),

r is an integer representing the number of repeats,

R²¹is a carbon atomAn alkylene group having a number of 1 to 6,

R²³is a linking group having a valence of 2,

z is a linking group having a valence of 3,

b are each independently an organic radical or Si (A)₃At least 1 of the 2 silyl groups is Si (A)₃The silyl groups as shown are those which, when considered,

said Si (A)₃Each of 3A's of the silyl group is independently a hydrolyzable group or a non-hydrolyzable group, and at least 1 of 3A's is a hydrolyzable group.

7. The structure according to any one of claims 1 to 3, wherein the fluorine-containing compound is a compound represented by the following formula (3),

in the formula (3), the reaction mixture is,

PFPE is a poly (perfluoroalkylene ether) chain,

Y¹and Y²Each independently being a direct bond or a 2-valent linking group,

Z¹and Z²Each independently a linking group having a valence of 2,

Si(A)₃each of 3A's of the silyl group is independently a hydrolyzable group or a non-hydrolyzable group, and at least 1 of 3A's is a hydrolyzable group.

8. The structure according to any one of claims 1 to 3, wherein the fluorine-containing compound is a compound represented by the following formula (4-1), (4-2) or (4-3),

in the above-mentioned formulae (4-1), (4-2) and (4-3),

r is an integer representing the number of repeats,

R⁴¹an alkylene group having 1 to 6 carbon atoms,

R⁴²is an alkyleneaminoalkylene or alkylenethioalkylene,

9. A structure according to any one of claims 4 to 8, wherein the hydrolyzable group is an alkoxy group.

10. The structure according to any one of claims 1 to 9, wherein the silicon-containing substance is an alkoxysilane compound.

11. The structure according to any one of claims 1 to 10, wherein the polymer having a polyethyleneimine skeleton is a fibrous polymer having a linear polyethyleneimine skeleton, the thickness of which is in the range of 10 to 200nm, and the length of which is in the range of 50nm to 2 μm.

12. The structure according to claim 11, wherein the long axis of the fibrous polymer having a linear polyethyleneimine skeleton is oriented in a direction substantially perpendicular to the surface of the base material.

13. The structure of claim 11, wherein the fibrous polymer having a linear polyethylenimine skeleton forms a network structure.

14. The structure according to any one of claims 1 to 13, wherein the base material is a resin base material or a metal base material.

15. The structure of any one of claims 1 to 14, wherein the substrate is an aluminum substrate.

16. The structure according to any one of claims 1 to 15, wherein a slip angle of water on the surface of the slip water-repellent layer is 5 ° or less.

17. A structure according to any one of claims 1 to 16, wherein the contact angle of water on the surface of the slip water-repellent layer is 160 ° or more.

18. A method of manufacturing a structure, comprising:

a step of bringing a base material into contact with a solution containing a polymer having a polyethyleneimine skeleton to form a layer containing the polymer having a polyethyleneimine skeleton on the surface of the base material;

a step of forming a silicon-containing substance in a layer containing the polymer having a polyethyleneimine skeleton by bringing a laminate containing the substrate and the layer containing the polymer having a polyethyleneimine skeleton into contact with a silicon-containing substance source liquid; and

and a step of treating the layer containing the polymer having a polyethyleneimine skeleton, on which the silicon-containing substance is formed, with a fluorine-containing compound.

19. A method of manufacturing a structure, comprising:

a step of forming a silicon-containing substance in a layer containing the polymer having a polyethyleneimine skeleton by bringing a laminate containing the substrate and the layer containing the polymer having a polyethyleneimine skeleton into contact with a silicon-containing substance source liquid;

a step of removing the polymer having a polyethyleneimine skeleton by baking a laminate comprising the base material and a layer containing the polymer having a polyethyleneimine skeleton and the silicon-containing substance; and

and a step of treating the layer containing a silicon-containing substance from which the polymer having a polyethyleneimine skeleton has been removed with a fluorine-containing compound.

20. A structure obtained by the production method according to claim 19,

the structure has a slip-off water-repellent layer on a substrate,

the slip water repellent layer comprises a fluorochemical and a siliceous material.

21. A heat exchanger member comprising the structure according to any one of claims 1 to 17 and 20.

22. A heat exchanger having a plurality of fins arranged in parallel with gaps provided therebetween, the fins having a slip water-repellent layer on a surface thereof, the slip water-repellent layer comprising: a polymer having a polyethyleneimine skeleton, a silane compound containing a silane compound having a perfluoroalkyl group and/or a perfluoropolyether group, and a silicon-containing substance.

23. The heat exchanger of claim 22, wherein the fins are aluminum fins.

24. An air conditioner or a cooler comprising the heat exchanger according to claim 22 or 23.