WO2021117537A1 - Member for fogging prevention, suppression of water droplet adhesion, suppression of icing, or suppression of ice nucleus formation - Google Patents

Abstract

A member for the suppression of water droplet adhesion, suppression of icing, or suppression of ice nucleus formation, has a layer that contains a brush-form polymer chain aggregation comprising a plurality of polymer chains immobilized to a substrate, wherein the layer containing the polymer chain aggregation holds a liquid substance.

Description

Member for anti-fog, suppression of water droplet adhesion, suppression of icing or suppression of ice nucleation

The present invention relates to an anti-fog member or a member for suppressing the adhesion of water droplets such as dew. The present invention also relates to an icing suppressing member that suppresses icing such as snow, ice, and frost. The present invention also relates to a member for suppressing ice nucleation that suppresses the formation and growth of ice nuclei.

When a colder surface comes into contact with warmer, moist air, the moisture in the atmosphere may condense on the colder surface, causing condensation or frost.

For example, in the fins of a heat exchanger such as an air conditioner, moisture in the atmosphere condenses during operation, the surface of the fins of the heat exchanger condenses and water droplets adhere, or frost is formed on the fin surface, resulting in heat. The fins of the exchanger may become clogged. Such clogging may increase ventilation resistance and reduce the exchange efficiency of the heat exchanger.

In order to prevent the occurrence of such a problem, for example, as described in Patent Document 1, a resin film is formed on the fin surface.

On the other hand, in recent years, research has been conducted on structures including brush-like polymer chain aggregates composed of a plurality of polymer chains, such as polymer brushes and bottle brushes. For example, lubricants for sliding members. (Patent Documents 2 and 3) and use as a narrowing gap material such as a laminated portion (Patent Document 4) have been proposed.

Japanese Unexamined Patent Publication No. 2015-131389 JP-A-2019-065284 International Publication No. 2017/171071 International Publication No. 2018/199181

However, conventionally known methods cannot sufficiently suppress the adhesion of water droplets and icing on the surface of the member, and there is room for further improvement. In addition, the formation and growth of ice nuclei on the surface of the member could not be sufficiently suppressed, and there was room for further improvement.

Patent Documents 2 to 4 describe inventions relating to brush-like polymer chain aggregates composed of a plurality of polymer chains, such as polymer brushes and bottle brushes, which are anti-fog and suppress water droplet adhesion. , There is no description about icing suppression and ice nucleation suppression.

Therefore, an object of the present invention is to provide a new member for antifogging, suppressing water droplet adhesion, suppressing icing, or suppressing ice nucleation.

When the present inventor diligently studied a brush-shaped polymer chain aggregate composed of a plurality of polymer chains fixed to a base material, a liquid substance was retained in the layer containing the above-mentioned polymer chain aggregate. It was found that water droplets such as dew did not easily adhere to the members. It was also found that the above members are less likely to cause icing such as snow, ice and frost. It was also found that water does not easily freeze on the surface of the above-mentioned member, and the formation and growth of ice nuclei can be suppressed. Based on such findings, the present invention has been completed. Therefore, the present invention proposes the following.
<1> A layer containing a brush-like polymer chain aggregate composed of a plurality of polymer chains fixed to a base material is provided, and the layer containing the polymer chain aggregate holds a liquid substance. ,
A member for anti-fog, suppression of water droplet adhesion, suppression of icing or suppression of ice nucleation.
<2> In <1>, the liquid substance is held in the layer containing the polymer chain aggregate and maintains the liquid state in the layer containing the polymer chain aggregate even at a temperature lower than the freezing point. The member described.
<3> The member according to <1> or <2>, wherein the liquid substance is water or an ionic liquid.
<4> The member according to any one of <1> to <3>, wherein the base material is a carrier made of a substance different from the polymer chain aggregate.
<5> The member according to <4>, wherein only one end of the polymer chains constituting the polymer chain aggregate is fixed to the base material.
<6> The member according to <4>, wherein both ends of the polymer chains constituting the polymer chain aggregate are fixed to the base material.
<7> The member according to any one of <4> to <6>, wherein the density of the polymer chains on the surface of the base material is 0.01 chains / nm ^{2 or more.}
<8> The base material is a polymer chain,
The member according to any one of <1> to <3>, wherein the plurality of polymer chains are bonded as side chains to the polymer chain which is the base material to form a polymer having a bottle brush structure. ..
<9> The member according to <8>, wherein the polymer having the bottle brush structure has a side chain density of 0.01 chain / nm ^{2 or more.}
<10> The member according to any one of <1> to <9>, wherein the film thickness of the layer containing the polymer chain aggregate is 350 nm or more.
<11> The member according to any one of <1> to <10>, wherein the contact angle of the surface of the member with water at 25 ° C. is 10 ° or more.

The present invention can provide a novel member for antifogging, suppressing water droplet adhesion, suppressing icing, or suppressing ice nucleation.

The numerical range represented by the symbol "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.

As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacryl", or , Means either.

<Members>
The member of the present invention
It has a layer containing a brush-like polymer chain aggregate composed of a plurality of polymer chains fixed to a base material.
The layer containing the polymer chain aggregate retains the liquid substance,
It is characterized by being a member for antifogging, suppressing water droplet adhesion, suppressing icing, or suppressing ice nucleation.

The member of the present invention has an excellent anti-fog effect, an effect of suppressing water droplet adhesion, an effect of suppressing icing, and an effect of suppressing ice nucleation. The detailed reason for obtaining such an effect is unknown, but it is presumed to be due to the following. In the member of the present invention, it is presumed that the liquid substance is held by the polymer chain aggregate to form a stable liquid layer in which irreversible liquid leakage is unlikely to occur in the layer containing the polymer chain aggregate. Will be done. Further, it is presumed that the liquid substance held in the polymer chain aggregate is likely to produce a supercooled state or an antifreeze state by appropriately controlling the motility by the polymer chain aggregate. It is presumed that the member of the present invention has an interface with high mobility against water droplets such as dew, ice, snow, frost, etc. due to the presence of such a stable liquid layer. Further, due to the existence of such a stable liquid layer, water can be thermally moved without solidification even below the freezing point, so that the freezing temperature of water on the surface of the member can be further lowered. It is presumed.
Since the member of the present invention has an interface with high mobility against water droplets such as dew, it is excellent in slipperiness such as water droplets on the surface of the member, and has an excellent antifogging effect and an effect of suppressing water droplet adhesion. Is presumed to have.
Further, the member of the present invention is less likely to freeze water on the surface of the member, is less likely to form ice, snow, frost, etc. on the surface of the member, and further has a highly mobile interface to ice, snow, frost, etc. Therefore, even if ice, snow, frost, etc. are formed on the surface of the member, they are excellent in slipperiness, and therefore, it is presumed that they have an excellent anti-icing effect.
Further, since the member of the present invention can further lower the freezing temperature of water inside or on the surface of the member, the temperature at which ice nuclei are generated can be lowered, and the member has an excellent ice nucleation suppressing effect. It is presumed that it is.

The polymer chain aggregate used in the present invention is an aggregate of a plurality of polymer chains and has a brush-like shape as a whole, and is formed by simply applying a polymer solution. It is completely different from the organic film. Further, it can be confirmed by differential scanning calorimetry that the layer containing the polymer chain aggregate retains the liquid substance. If it cannot be confirmed by differential scanning calorimetry, it can be confirmed by the method of indentation hardness test (indentation test).

In the member of the present invention, the liquid substance is held in the layer containing the polymer chain aggregate and has a temperature lower than the freezing point (preferably −10 ° C. or lower, more preferably −20 ° C. or lower, still more preferably −30 ° C. or lower). ) But it is preferable to keep the liquid state. Further, the liquid substance is preferably water. Whether or not the liquid substance is in a liquid state can be confirmed by differential scanning calorimetry. If it cannot be confirmed by differential scanning calorimetry, it can be confirmed by the method of indentation hardness test (indentation test).

In the member of the present invention, the thickness of the layer containing the polymer chain aggregate is 50 nm because more excellent antifogging effect, water droplet adhesion suppressing effect, icing suppressing effect and ice nucleation suppressing effect can be easily obtained. It is preferably 100 nm or more, more preferably 350 nm or more, further preferably 500 nm or more, and particularly preferably 1000 nm or more. The upper limit is not particularly limited, but can be, for example, 100 μm or less, or 50 μm or less.

When the member of the present invention is an anti-fog member or a member for suppressing water droplet adhesion, it is preferably 50 nm or more, preferably 100 nm or more, because a more excellent anti-fog effect and water droplet adhesion suppressing effect can be easily obtained. Is more preferably 350 nm or more, further preferably 500 nm or more, and particularly preferably 1000 nm or more. The upper limit is not particularly limited, but can be, for example, 100 μm or less, or 50 μm or less.

When the member of the present invention is a member for suppressing icing, it is preferably 50 nm or more, more preferably 100 nm or more, and 350 nm or more because it is easy to obtain a better icing suppressing effect. It is even more preferably 500 nm or more, and particularly preferably 1000 nm or more. The upper limit is not particularly limited, but can be, for example, 100 μm or less, or 50 μm or less.

When the member of the present invention is a member for suppressing ice nucleation, it is preferably 50 nm or more, more preferably 100 nm or more, and 350 nm, because a more excellent ice nucleation suppressing effect can be easily obtained. The above is more preferable, 500 nm or more is even more preferable, and 1000 nm or more is particularly preferable. The upper limit is not particularly limited, but can be, for example, 100 μm or less, or 50 μm or less.

The film thickness of the layer containing the polymer chain aggregate can be measured by spectroscopic ellipsometry or the like.

Hereinafter, the members of the present invention will be described in detail.

[Polymer chain aggregate]
The polymer chain aggregate in the present invention is composed of a plurality of polymer chains and has a brush-like shape as a whole. The "polymer chain" in the present invention refers to a molecule or a portion of a molecule having a structure in which a plurality of structural units are linked in a chain. The plurality of polymer chains constituting the polymer chain aggregate may be the same as or different from each other. Further, the polymer chain may have a structure in which a plurality of structural units are connected in a chain shape, and may have a side chain or a branched structure, and is between the polymer chains. A crosslinked structure may be formed between the polymer chain and the base material.

(Polymer chain)
The polymer chain preferably has an affinity for a liquid substance to be retained in the layer containing the polymer chain aggregate. For example, when water or a hydrophilic liquid substance is retained in a layer containing a polymer chain aggregate, the polymer chain constituting the polymer chain aggregate is preferably a hydrophilic polymer chain. The hydrophilic polymer chain may be synthesized using a hydrophilic monomer, or may be synthesized by synthesizing a polymer using a hydrophobic monomer and then introducing a hydrophilic group into the polymer.

The polymer chain may be a homopolymer obtained by polymerizing one type of monomer, or may be a copolymer obtained by polymerizing two or more types of monomers. Examples of the copolymer include a random copolymer, a block copolymer, a gradient copolymer and the like.

The monomer used to generate the polymer chain is preferably one that can bond the polymer chain obtained by the polymerization to the base material as a graft chain. Examples of such a monomer include a monomer having at least one addition-polymerizable double bond, and a monofunctional monomer having one addition-polymerizable double bond is preferable. Examples of the monofunctional monomer having one addition-polymerizable double bond include (meth) acrylic acid-based monomers and styrene-based monomers.

Examples of the (meth) acrylic acid-based monomer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth). Acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl ( Meta) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) Acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 3-ethyl-3- (meth) Acryloyloxymethyloxetane, 2- (meth) acryloyloxyethyl isocyanate, (meth) acrylate-2-aminoethyl, 2- (2-bromopropionyloxy) ethyl (meth) acrylate, 2- (2-bromoisobutyryloxy) ) Ethyl (meth) acrylate, 1- (meth) acryloxy-2-phenyl-2- (2,2,6,6-tetramethyl-1-piperidinyloxy) ethane, 1-(4-((4-(4-) (Meta) acryloxy) ethoxyethyl) phenylethoxy) piperidine, γ- (methacryloyloxypropyl) trimethoxysilane, 3- (3,5,7,9,11,13,15-heptaethylpentacyclo [9.5. 1.13, 9.15, 15.17, 13] Octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15-heptaisobutyl-pentacyclo [9] .5.1.13, 9.15, 15.17, 13] Octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15-heptaisooctyl) Pentacyclo [9.5.1.13, 9.15, 15.17, 13] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11) , 13,15-Heptacyclopentylpentacyclo [9.5.1.13, 9.15, 15.17,13] Octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7, 9,11,13,15-Heptaphenylpentacyclo [9.5.1.13, 9.15, 15.17,13] octasiloxane-1-yl) propyl (meth) acrylate, 3-[(3,3) 5,7,9,11,13,15-Heptaethylpentacyclo [9.5.1.13,9.15,15.17,13] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate , 3-[(3,5,7,9,11,13,15-heptaisobutylpentacyclo [9.5.1.13,9.15,15.17,13] octasiloxane-1-yloxy) dimethyl Cyril] propyl (meth) acrylate, 3-[(3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1.13, 9.15, 15.17, 13]] Octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3-[(3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.13, 9.15] , 15.17,13] Octasiloxane-1-yloxy) Dimethylsilyl] propyl (meth) acrylate, 3-[(3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5. 1.13, 9.15, 15.17, 13] Octasiloxane-1-yloxy) Dimethylsilyl] Propyl (meth) acrylate, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-Trifluoromethylethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, trifluoromethyl (meth) ) Acrylic, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, 2-perfluorohexyl ethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro Hexadecylethyl (meth) acrylate and the like can be mentioned.

Examples of styrene-based monomers include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, m-chloromethylstyrene, o-aminostyrene, p-styrenechlorosulfonic acid, styrenesulfonic acid and the like. Salt, vinylphenylmethyldithiocarbamate, 2- (2-bromopropionyloxy) styrene, 2- (2-bromoisobutyryloxy) styrene, 1-(2-((4-vinylphenyl) methoxy) -1-phenyl Ethoxy) -2,2,6,6-tetramethylpiperidine, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.13 , 9.15, 15.17, 13] Octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaisobutylpentacyclo [9.5.1.13 9.15, 15.17, 13] Octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1.13 9.15, 15.17, 13] Octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.13, 9] .15, 15.17, 13] Octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-Heptaphenylpentacyclo [9.5.1.13, 9. 15, 15.17, 13] Octasiloxane, 3- (3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.13, 9.15, 15.17, 13] ] Octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13,15-heptaisobutylpentacyclo [9.5.1.13, 9.15, 15.17, 13] ] Octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1.13, 9.15, 15.17, 13] Octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.13, 9.15, 15.17, 13] Octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5.1.13, 9.15, 15.17, 13] Octasiloxane-1-yl) ethylstyrene, 3-((3,5,7,9,11,13,15-heptaethylpentacyclo] [9.5.1.13, 9.15, 15.17] , 13] Octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3-((3,5,7,9,11,13,15-heptaisobutylpentacyclo [9.5.1.13, 9.15] , 15.17,13] Octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3-((3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1. 13,9.15,15.17,13] Octasiloxane-1-yloxy) Dimethylsilyl) Ethylstyrene, 3-((3,5,7,9,11,13,15-Heptacyclopentylpentacyclo [9. 5.1.13, 9.15, 15.17, 13] Octasiloxane-1-yloxy) Dimethylsilyl) Ethylstyrene, 3-((3,5,7,9,11,13,15-Heptaphenylpenta) Cyclo [9.5.1.13, 9.15, 15.17, 13] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene and the like can be mentioned.

Further, as a monofunctional monomer having one addition-polymerizable double bond in one molecule, a fluorine-containing vinyl monomer (perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc.) and a silicon-containing vinyl-based monomer (vinyltrimethoxy) Silane, vinyl triethoxysilane, etc.), maleic anhydride, maleic acid, maleic acid monoalkyl and dialkyl esters, fumaric acid, fumaric acid monoalkyl and dialkyl esters, maleimide-based monomers (maleimide, methylmaleimide, ethylmaleimide) , Ppropylmaleimide, Butylmaleimide, Hexylmaleimide, Octylmaleimide, Dodecylmaleimide, Stearylmaleimide, Phenylmaleimide, Cyclohexylmaleimide, etc.), Nitrile group-containing monomers (acrylonitrile, methacrylonitrile, etc.), Amido group-containing monomers (acrylamide, methacrylicamide, etc.) ), Vinyl ester-based monomers (vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnate, etc.), olefins (ethylene, propylene, etc.), conjugated diene-based monomers (butadiene, isoprene, etc.), halogenation Vinyl (vinyl chloride, etc.), vinylidene halide (vinylidene chloride, etc.), allyl halide (allyl chloride, etc.), allyl alcohol, vinylpyrrolidone, vinylpyridine, N-vinylcarbazole, methylvinylketone, vinylisocyanate, main chain Macromonomers derived from styrene, (meth) acrylic acid ester, siloxane and the like can also be used.

It is also preferable to use an ionic liquid monomer for the formation of polymer chains. The ionic liquid monomer is not particularly limited, and examples thereof include a compound represented by the following formula (1).

In the formula (1), m represents an integer of 1 to 10, and n represents an integer of 1 to 5. R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 5 carbon atoms. However, the ^{alkyl group in R 2} , R ³ and R ⁴ may have its carbon atom or hydrogen atom substituted with one or more hetero atoms selected from oxygen atom, sulfur atom and fluorine atom, and R ² , R ³ and R ⁴ may be connected by two or more to form an annular structure.

Y represents a monovalent anion. Examples of the monovalent anion Y represents is not particularly limited, for example, _{^{BF 4 -, PF 6 -,}} AsF 6 -, SbF 6 -, AlCl 4 -, NbF 6 -, HSO 4 -, ClO 4 -, CH 3 _{^{SO 3 -, CF 3 SO 3}} -, CF 3 CO 2 -, (CF 3 SO 2) 2 N -, Cl -, Br -, I - , and the like can be given. Considering the stability of the _{^{anion, BF 4 -, PF 6 -}} , (CF 3 SO 2) 2 N -, CF 3 SO 3 -, or _CF 3 CO ₂ ^- is preferably.

Among the compounds represented by the formula (1), the ionic liquid monomer is particularly preferably a compound represented by any of the following formulas (2) to (9).

In the formula ^{(2) ~ (9),} m, R 1, R 2, Y has the same meaning as ^m, R ^{1, R} 2, Y of formula (1). Me represents a methyl group and Et represents an ethyl group.

It is preferable to use a hydrophilic monomer for the formation of a hydrophilic polymer chain. That is, the hydrophilic polymer chain preferably contains a repeating unit derived from a hydrophilic monomer.

Hydrophilic monomers include hydroxy-substituted alkyl (meth) acrylates (eg, 2-hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates, 2,3-dihydroxypropyl (eg). Meta) acrylate, polyethoxyethyl (meth) acrylate, polyethoxypropyl (meth) acrylate, etc.), poly (alkylene glycol) mono (meth) acrylate (eg, poly (ethylene glycol) monomethacrylate, etc.), alkoxypoly (alkylene glycol, etc.) ) (Meta) acrylate (eg, methoxypoly (ethylene glycol) methacrylate, etc.), phenoxypoly (alkylene glycol) (meth) acrylate (eg, phenoxypoly (ethylene glycol) methacrylate, etc.) are preferable, and polyalkoxypoly (alkylene glycol) ( Meta) acrylate is more preferred.

Examples of the hydrophilic monomer include (meth) acrylamide, N-alkyl (meth) acrylamide (eg, N-methylacrylamide, N, N-dimethylacrylamide, N-methylmethacrylamide, etc.) and 2-glucosyloxyethyl (meth). ) Use acrylate, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, methacrylamide, N-vinylpyrrolidone, N, N-dimethylaminoethyl (meth) acrylate, and quaternary ammonium salts thereof. You can also.

For the formation of the hydrophilic polymer chain, it is also preferable to use a monomer having a carboxyl group or a group that can be easily converted into a salt of the carboxyl group in the side chain. Hydrophilicity can be imparted by converting the side chain group of the produced polymer chain into a carboxyl group or a salt of the carboxyl group. Examples of the monomer having a carboxyl group or a group having a group that can be easily converted into a salt of the carboxyl group in the side chain include tert-butyl (meth) acrylate and the like.

As the monomer used for producing these polymer chains, one type may be used alone, or two or more types may be used in combination.

The polymer chain aggregate may have a crosslinked structure formed between the polymer chains or between the polymer chains and the base material. Thereby, the elastic modulus of the polymer chain aggregate can be controlled. The crosslinked structure formed between the polymer chains may be either a physical crosslinked structure or a chemically crosslinked structure. The crosslinked structure may be formed at the same time as the polymerization reaction for forming the polymer chain, or may be formed after the polymer chain is formed. The formation of the crosslinked structure performed at the same time as the polymerization reaction for forming the polymer chain is performed in the polymerization reaction solution like a divinyl monomer such as ethylene glycol dimethacrylate in addition to the monofunctional monomer for forming the polymer chain. It can be carried out by adding an appropriate amount of a bifunctional monomer. Further, in order to form a crosslinked structure between the generated polymer chains or between the polymer chain and the base material, a crosslinked group is introduced into the polymer chain using a monomer having a crosslinked group, and the crosslinked group is introduced. And the reaction with the reactive group of another polymer chain, and the reaction between the cross-linking group and the reactive group of the base material. Examples of the cross-linking group include an azide group, a halogen group (preferably a bromo group), an alkoxysilyl group, an isocyanate group, a vinyl group, a thiol group and the like. Further, when the polymer chain is produced by living radical polymerization, the reactive group remaining at the end of the graft chain can also be used as a cross-linking group.

In the member of the present invention, the polymer chains constituting the polymer chain aggregate are fixed to the base material. The base material may be a carrier made of a substance different from the polymer chain aggregate, or may be a polymer chain as a main chain in which the polymer chains are bonded as side chains. When the substrate is a carrier, the polymer chain aggregate constitutes a "polymer brush". When the base material is a polymer chain, the entire main chain composed of the polymer chain and the polymer chain (side chain) bonded to the main chain are combined to form a "polymer having a bottle brush structure". Configure. Further, when the polymer chains constituting the polymer chain aggregate are fixed to a carrier made of a substance different from the polymer chain aggregate, that is, the polymer chain aggregate constitutes the "polymer brush". In this case, only one end of the polymer chain may be fixed to the base material (carrier), or both ends of the polymer chain may be fixed to the base material (carrier). When both ends of the polymer chain are fixed to the base material (carrier), the polymer chain has a loop structure, and such a polymer chain aggregate forms a polymer brush having a loop structure. ..

In the member of the present invention, when the polymer chain aggregate constitutes the polymer brush, the film thickness of the polymer brush, that is, the film thickness of the polymer chain aggregate is preferably 50 nm or more, preferably 100 nm or more. It is more preferably 300 nm or more, further preferably 500 nm or more, and particularly preferably 1000 nm or more. The upper limit is not particularly limited, but can be, for example, 100 μm or less, or 50 μm or less.

Further, in the member of the present invention, the polymer chain aggregate is bonded as a side chain of the polymer chain, and the main chain formed by the polymer chain and the polymer chain (side chain) bonded to the main chain are combined. When the whole constitutes a "polymer having a bottle brush structure", the thickness of the layer containing the polymer having a bottle brush structure is preferably 50 nm or more, more preferably 100 nm or more, and more preferably 300 nm. The above is more preferable, 500 nm or more is even more preferable, and 1000 nm or more is particularly preferable. The upper limit is not particularly limited, but can be, for example, 100 μm or less, or 50 μm or less.

In the following, a method for forming a polymer chain aggregate will be described for each of the polymer brush and the polymer having a bottle brush structure.

[A] Polymer Brush The polymer chain aggregate of the polymer brush can be obtained by a graft polymerization method in which a plurality of polymer chains are bonded to a carrier as a base material as graft chains. This graft polymerization can be carried out by the Grafting-from method or the Grafting-to method, and it is preferable to use the Grafting-from method. Here, the Grafting-from method is a method in which a polymerization initiating group is introduced into a base material and a graft chain is grown from the polymerization initiating group, and the Grafting-to method uses a graft chain synthesized in advance as a base material. It is a method of binding to the introduced reaction site.
Further, in the polymer chain aggregate, the hydrophobic portion of a polymer (diblock copolymer) having a hydrophobic block and a hydrophilic block is made hydrophobic on the surface of a hydrophobic base material or a hydrophobic base material. It can also be obtained by the method of combining. Examples of the diblock copolymer include a copolymer having a polymethylmethacrylate (PMMA) structure as a hydrophobic block and a poly (sodium sulfonated glycidyl methacrylate) (PSGMA) structure as a hydrophilic block. Other polymer structures may intervene between the PMMA structure and the PSGMA structure. For more information on this method, see Nature, 425, 163-165 (2003) and the like.

(Graft polymerization method)
Hereinafter, a method for forming the polymer chain aggregate by using the graft polymerization method will be specifically described.

Polymer chain formation The polymer chain formation method used in the graft polymerization method is not particularly limited, but it is preferable to use a radical polymerization method, more preferably a living radical polymerization method (LRP) method, and atom transfer radicals. It is more preferred to use the polymerization (ATRP) method. The living radical polymerization method grafts various types of copolymers (eg, random copolymers, block copolymers, composition-inclined copolymers, etc.) that can easily control the molecular weight and molecular weight distribution of the polymer chains. It has the advantage that it can be generated as. Further, according to the living radical polymerization method, by using high pressure conditions or an ionic liquid solvent, it is possible to produce a concentrated polymer brush described later by precisely controlling the density and thickness thereof. Here, the graft polymerization method when the living radical polymerization method is used may be either the Grafting-from method or the Grafting-to method, but the Grafting-from method is preferable. For details of the graft polymerization method in which the living radical polymerization method and the Grafting-from method are combined, Japanese Patent Application Laid-Open No. 11-263819 and the like can be referred to. For details of the atom transfer radical polymerization method, refer to J.M. Am. Chem. Soc. , 117, 5614 (1995), Macromolecules, 28, 7901 (1995), Science, 272, 866 (1996), Macromolecules, 31, 5934-5936 (1998).
The polymer chain is also produced by a nitroxide-mediated polymerization method (NMP), a reversible addition cleavage chain transfer (RAFT) polymerization method, a reversible transfer catalyst polymerization method (RTCP), a reversible complex formation-mediated polymerization method (RCMP), or the like. can do.

The catalyst used in the radical polymerization method may be any catalyst capable of controlling radical polymerization, and is preferably a transition metal complex. Preferred examples of the transition metal complex include metal complexes having Group 7, 8, 9, 10 or 11 elements of the periodic table as the central metal, among which copper complex, ruthenium complex and iron. It is preferable to use a complex or a nickel complex, and it is more preferable to use a copper complex. The copper complex is preferably a complex of a monovalent copper compound and an organic ligand. Examples of the monovalent copper compound include cuprous chloride, cuprous bromide and the like. As organic ligands, 2,2'-bipyridyl or its derivatives, 1,10-phenanthroline or its derivatives, polyamines (tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amines, etc.), L- (-)-Polycyclic alkaloids such as spartane can be mentioned. A triphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, it is preferable to add aluminum alkoxides as an activator. Divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), divalent nickel bistributylphosphine complex (NiBr ₂₎ (PBu ₃ ) ₂ ) and the like are also suitable as catalysts.

The polymerization reaction is preferably carried out in a solvent. As solvents, hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (methylene chloride, chloroform, chlorobenzene, etc.), ketones Solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol, t-butyl alcohol, etc.), nitrile solvents (acetriform, propionitrile, benzonitrile, etc.), esters System solvents (ethyl acetate, butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents (N, N-dimethylformamide, N, N-dimethylacetamide), hydrochlorofluorocarbon solvents (1, 1-dichloro-1-fluoroethane, dichloropentafluoropropane), hydrofluorocarbon solvent (hydrofluorocarbon with 2 to 5 carbon atoms, hydrofluorocarbon with 6 or more carbon atoms and 6 or more carbon atoms), perfluorocarbon solvent (perfluoropentane, Perfluorohexane), alicyclic hydrofluorocarbon solvent (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorosolvent (fluoroether, fluoropolyether, fluoroketone, fluoroalcohol), water and the like. One type of these solvents may be used alone, or two or more types may be used in combination.

Introduction of Polymerization Initiator In order to form an aggregate of polymer chains by using, for example, the Grafting-from method, a polymerization initiator group which is a starting point of a polymerization reaction is introduced into a substrate, and the above-mentioned polymerization is carried out from this polymerization initiator group. Polymer chains are graft grown using the method. Examples of the polymerization initiating group include an alkyl halide group and a sulfonyl halide group. Since the polymerization initiator can accurately control the density of the graft chain (graft density) and the primary structure (molecular weight, molecular weight distribution, monomer arrangement mode) of the polymer chain obtained by graft polymerization, it can be physically or chemically applied to the surface of the substrate. It is preferable that they are bonded to each other. Examples of the method for introducing (bonding) the polymerization initiating group to the surface of the substrate include a chemisorption method, a Langmuir Brodget (LB) method and the like.
For example, introduction of a chlorosulfonyl group (polymerization initiator group) onto the surface of a silicon wafer (base material) by a chemical bond is performed with 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane or 2- (4-chlorosulfonylphenyl) ethyl. This can be done by reacting trichlorosilane or the like with an oxide layer on the surface of a silicon wafer.

Further, in order to introduce the polymerization initiating group by the LB method, the film-forming material containing the polymerization initiating group is dissolved in an appropriate solvent (eg, chloroform, benzene, etc.). Next, a small amount of this solution is developed on a clean liquid surface, preferably pure water, and then the solvent is evaporated or diffused into an adjacent aqueous phase to have a low density of film-forming molecules on the water surface. To form a film. Subsequently, the partition plate is mechanically swept over the water surface to compress the membrane by reducing the surface area of the water surface on which the film-forming molecules are developed to increase the density, and obtain a dense monomolecular film on the water surface. .. Then, under appropriate conditions, the base material on which the monolayer is deposited is immersed or pulled up in a direction crossing the monolayer on the water surface while keeping the surface density of the molecules constituting the monolayer on the water surface constant. , The monomolecular film on the water surface is transferred onto the base material, and the monomolecular layer is deposited on the base material. For details on the LB method, see "Kiyonari Fukuda et al., New Experimental Chemistry Course Volume 18 (Interface and Colloid) Chapter 6, (1977) Maruzen", "Kiyonari Fukuda, Michio Sugi, Hiroyuki Sasabe, LB Membrane" You can refer to "Electronics, (1986) CMC" or "Practical Techniques for Making Good LB Films, (1989) Kyoritsu Shuppan" by Yoshio Ishii.

When introducing a polymerization initiator group into the surface of a substrate, at least one of a group bonded to the substrate and a group having an affinity with the substrate, and a group having an affinity with the group bonded to the polymerization initiator group and the polymerization initiator group are used. It is preferable to treat the surface of the base material with a surface treatment agent having at least one of the above. This surface treatment agent may be a low molecular weight compound or a high molecular weight compound. Examples of the surface treatment agent include compounds represented by the following formula (10).

In the formula (10), n is an integer of 1 to 10, preferably an integer of 3 to 8. R ¹¹ , R ¹² and R ¹³ each independently represent a substituent. At ^{least one of R 11} , R ¹² and R ¹³ is preferably an alkoxyl group or a halogen atom, and it is particularly preferable that all of ^{R 11} , R ¹² and R ^{13 are methoxy groups or ethoxy groups.} .. R ¹⁴ and R ¹⁵ each independently represent a substituent. R ¹⁴ and R ¹⁵ are preferably alkyl groups having 1 to 3 carbon atoms or aromatic functional groups, respectively, ^{and most preferably both R 14} and R ¹⁵ are methyl groups. X ¹¹ represents a halogen atom and is preferably a bromine atom.

As the surface treatment agent, it is preferable to use a silane coupling agent containing a polymerization initiating group (a silane coupling agent containing a polymerization initiating group). Thereby, the surface treatment and the introduction of the polymerization initiating group can be performed at the same time. Examples of the polymerization initiating group-containing silane coupling agent include compounds represented by the above formula (1). For a description of the polymerization initiating group-containing silane coupling agent and a method for producing the same, the description of International Publication No. 2006/087839 can be referred to. Specific examples of the polymerization initiator-containing silane coupling agent include (2-bromo-2-methyl) propionyloxyhexyltrimethoxysilane (BHM) and (2-bromo-2-methyl) propionyloxypropyltrimethoxysilane (BPM). Can be mentioned.

When a polymerization initiating group-containing silane coupling agent is used as a surface treatment agent from the viewpoint of adjusting the graft density, a silane coupling agent that does not contain a polymerization initiating group, for example, a known alkylsilane coupling agent should be used in combination. Is preferable. Thereby, the graft density can be freely changed by adjusting the ratio of the silane coupling agent containing a polymerization initiating group and the silane coupling agent not containing a polymerization initiating group. For example, when all of the silane coupling agents are polymerization initiation group-containing silane coupling agents, the polymer chains are formed with a surface occupancy rate of more than 3% by performing graft polymerization by the Grafting-from method after the surface treatment thereof. Can grow. When a polymerization initiating group-containing silane coupling agent is used as the surface treatment agent, the polymerization initiating group-containing silane coupling agent is hydrolyzed in the presence of water to form silanol, which is partially condensed to form an oligomer state. After that, it may be subjected to surface treatment. Specifically, this oligomer may be adsorbed on a base material such as silica in a hydrogen-bonding manner and then subjected to a drying treatment to cause a dehydration condensation reaction, and a polymerization initiating group may be introduced into the base material.

(Base material)
In the polymer brush type polymer chain aggregate, the material constituting the base material (carrier) for fixing the polymer chain is not particularly limited. It can be appropriately selected from organic materials, inorganic materials, metal materials and the like.

The organic material is not particularly limited, and various resins and rubbers can be used without limitation. The resin may be either a thermosetting resin or a thermoplastic resin. Examples of the thermosetting resin include epoxy resin, phenol resin, amino resin, unsaturated polyester resin, polyurethane resin, urea resin, melamine resin, thermosetting polyimide resin, diallyl phthalate resin and the like. Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, polystyrene and polycycloolefin; vinyl resins such as polystyrene, acrylic resin, polyvinyl chloride resin and polyvinyl alcohol; and fluororesins such as polytetrafluoroethylene. Polyester-based resins such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polyethylene naphthalate; silicone resins such as polydimethylsiloxane; and the like. As rubber, diene rubber such as butadiene rubber, styrene butadiene rubber, chloroprene rubber, isoprene rubber, natural rubber, nitrile rubber, butyl rubber; ethylene propylene rubber, acrylic rubber, polyether rubber, polyurethane rubber, fluororubber, silicone rubber, etc. Examples include rubbers other than the diene rubber.

The inorganic material is not particularly limited, and is limited to ceramics (eg, alumina ceramics, bioceramics, composite ceramics such as zirconia-alumina composite ceramics, etc.), metals (eg, iron, cast iron, steel, stainless steel, carbon steel, high carbon). Iron alloys such as chrome bearing steel (SUJ2), non-iron and non-iron alloys such as aluminum, zinc, copper and titanium), silicon such as polycrystalline silicon, silicon oxide, silicon nitride, various glasses, quartz, and composites thereof. Materials and the like can be mentioned.

The type of base material is not particularly limited. For example, tubes, sheets, fibers, strips, films, plates, foils, membranes, pellets, powders, particles, molded products (eg, extruded products, cast molded products, etc.) and the like can be mentioned. Further, the article itself to which the member of the present invention is applied may be used as the base material.

(Other manufacturing methods)
Further, the polymer chain aggregate of the polymer brush can also be produced by the following production method. That is, the organic material constituting the base material (hereinafter, also referred to as the base material polymer) and the polymer block A and the polymer block B having a lower affinity for the base material polymer than the polymer block A are provided. A step of preparing a mixed solution by mixing a plurality of block copolymers having polymer blocks A at at least two positions in a solvent, and a step of removing the solvent from the mixed solution to cause phase separation. It can be manufactured by a manufacturing method including. According to this production method, it is possible to produce a polymer chain aggregate of a loop structure polymer brush in which both ends of the polymer chains constituting the polymer chain aggregate are fixed to a substrate which is a carrier. it can.

The organic material constituting the base material, which is a base material polymer, is not particularly limited, and the above-mentioned ones can be mentioned.

The block copolymer includes a polymer block A and a polymer block B having a lower affinity for the base polymer than the polymer block A, and has the polymer blocks A at at least two locations. It is good, but not particularly limited, from the viewpoint that a loop structure can be preferably formed, it is preferable to use a polymer block B that is incompatible with the base polymer, and the polymer block B has a base weight. A combination that is incompatible with the coalescence and the polymer block A is compatible with the base polymer is more preferable.

Here, the fact that the polymer block A is compatible with the base polymer means the following state. That is, it is obtained by mixing a polymer composed of only the polymer block A and a base polymer by hot melt mixing or co-solution mixing, and then solidifying the obtained mixture by cooling or solvent evaporation removal. When the glass transition temperature (Tg) of the sample was measured, Tg different from these was observed in the temperature range between the Tg of the polymer consisting only of the polymer block A and the Tg of the base polymer. If possible, it can be determined to be compatible.

Further, the fact that the polymer block B is incompatible with the base polymer means the following state. That is, it is obtained by mixing a polymer composed of only the polymer block B and a base polymer by hot melt mixing or co-solution mixing, and then solidifying the obtained mixture by cooling or solvent evaporation removal. When the glass transition temperature (Tg) of the obtained sample is measured, if Tg different from the Tg of the polymer consisting only of the polymer block B and the Tg of the base polymer 20 cannot be observed, it is not observed. It can be judged that they are compatible.

As the polymer block A and the polymer block B, those having the above-mentioned compatibility with the base polymer may be used, but from the viewpoint that a loop structure can be preferably formed, these SP values (solubility parameters) are related. The difference between the SP value of the polymer block A and the SP value of the polymer block B ^{is preferably 1.5 (MPa) 0.5} or more, and more preferably 3 (MPa) ^0.5 or more. It is more preferably 5 (MPa) ^{0.5 or more.} Further, regarding the SP value of the polymer block A, the difference between the SP value of the polymer block A and the SP value of the base polymer ^{is preferably 0.5 (MPa) 0.5} or less, and is 0.3 ( MPa) ^0.5 or less is more preferable, and 0.2 (MPa) ^0.5 or less is further preferable. Regarding the SP value of the polymer block B, the difference between the SP value of the polymer block B and the SP value of the base polymer ^{is preferably 1.5 (MPa) 0.5} or more, and 3 (MPa) ^0.5. The above is more preferable, and 5 (MPa) ^0.5 or more is further preferable. As the SP values of the polymer block A and the polymer block B, for example, the values disclosed in the Polymer Handbook (4th edition, Wiley-Interscience) can be used.

The polymer block A may be selected as long as it satisfies the above-mentioned characteristics, and is not particularly limited, and may be selected in relation to the base material polymer to be used. As a specific example thereof, the above-mentioned base material polymer may be used. Examples of the constituent resin or rubber include those composed of polymer segments constituting the resin or rubber exemplified.

The molecular weight (weight average molecular weight (Mw)) of the polymer block A portion of the block copolymer is not particularly limited, but exhibits sufficient interaction with the base polymer, thereby forming a loop structure formed by the polymer block B. From the viewpoint that durability can be further enhanced by more appropriately supporting the above, preferably 1,000 to 100,000, more preferably 1,000 to 50,000, still more preferably 1,000 to 20, It is 000, more preferably 2,000 to 20,000, and particularly preferably 2,000 to 6,000.

As the polymer block B, among those described as the above-mentioned polymer chains, those that satisfy the above-mentioned characteristics with the base polymer are preferably used.

The solvent used when mixing the base polymer and a plurality of block copolymer chains in a solvent is not particularly limited, and the base polymer and the block copolymer chains can be dissolved or dispersed. Any solvent can be used. For example, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane. , Hexahydroindene, alicyclic hydrocarbons such as cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene, mesityrene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, acetonitrile, propionitrile, benzonitrile; diethyl Ethers such as ether, tetrahydrofuran, dioxane; ketones such as acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone; esters such as methyl acetate, ethyl acetate, ethyl propionate, methyl benzoate; chloroform, Halogenized hydrocarbons such as dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene and trichlorobenzene; alcohols such as methanol and ethanol can be mentioned.

A mixed solution can be obtained by mixing, dissolving or dispersing the base polymer and a plurality of block copolymer chains in such a solvent. Next, the obtained mixed solution is used to form a film by a casting method, a spin coating method, or the like, and then the solvent is removed from the formed mixed solution. A part of the plurality of block copolymer chains dispersed with respect to the base polymer via the solvent was removed from the base polymer, so that the polymer block A was compatible with the base polymer. In the state, the polymer block B constituting the block copolymer chain is phase-separated from the base material polymer, the polymer block A is in the base material polymer, and the polymer block B is the base material weight. It can be changed from coalescence to an exposed state, whereby a loop structure in which both ends of the polymer chains constituting the polymer chain aggregate are fixed to the carrier can be formed.

The method for removing the solvent is not particularly limited and may be selected according to the type of solvent used, but a method of heating at 50 ° C. to 100 ° C. is preferable, and a method of heating at 70 to 80 ° C. is more preferable. preferable.

Further, the polymer chain aggregate of the polymer brush can also be manufactured by the following manufacturing method. That is, a plurality of blocks including the base polymer and the polymer block A and the polymer block B having a lower affinity for the base polymer than the polymer block A, and having the polymer blocks A at at least two locations. It can also be produced by a production method including a step of preparing a molten mixture by mixing the copolymer under heating and a step of causing phase separation by cooling the molten mixture. Also by this production method, it is possible to produce a polymer chain aggregate of a loop structure polymer brush in which both ends of the polymer chains constituting the polymer chain aggregate are fixed to a base material which is a carrier. ..

The heating temperature when the base polymer and a plurality of block copolymers are mixed under heating to prepare a melt mixture is not particularly limited, and is the temperature at which the base polymer or the block copolymer melts. The temperature at which both the base polymer and the block copolymer chain are melted may be preferably set to 40 to 300 ° C, more preferably 80 to 200 ° C.

Using the obtained melt mixture, a film is formed by a casting method, a spin coating method, a dip coating method, etc., and then cooled, and phase separation occurs in the process of solidification by cooling. In the process in which a part of the plurality of block copolymers dispersed with respect to the substrate polymer is changed from the molten state to the solid state by being melt-mixed, the substrate weight of the polymer block A is increased. The polymer block B constituting the block copolymer is phase-separated from the base polymer while remaining in a state of being compatible with the coalescence, so that the polymer block A is present in the base polymer and the polymer block. B can be changed to an exposed state from the base polymer, whereby a loop structure can be formed.

The method for cooling the melt mixture is not particularly limited, but a method of allowing the formed melt mixture to stand at room temperature or a method of allowing the formed melt mixture to stand still at a temperature lower than the melt temperature of each component constituting the melt mixture. The method of placing it can be mentioned.

(Number average molecular weight and molecular weight distribution index of polymer chains)
_{The number average molecular weight (Mn} ) of the polymer chains constituting the polymer chain aggregate is preferably 500 to 10,000,000, more preferably 100,000 to 10,000,000.
The molecular weight distribution index (PDI = M _w / M _n ) in the polymer chain aggregate is preferably 1.0 to 2.0, more preferably 1.0 to 1.5. When the molecular weight distribution index is within the above range, the effect of maintaining a high-density state up to the outermost surface of the polymer chains constituting the polymer chain aggregate can be expected.

The number average molecular weight (M _n ) and molecular weight distribution index (M _w / M _n ) of the polymer chain aggregate are obtained by cutting out the polymer chain from the substrate by hydrofluoric acid treatment and gel permeation chromatography on the cut out polymer chain. It can be measured by performing molecular weight analysis by a size exclusion chromatography method such as a imaging method.

Further, when a polymer chain aggregate is formed by using the graft polymerization method, it is assumed that the free polymer produced during the polymerization reaction of the polymer chains has a molecular weight equal to that of the polymer chains fixed to the substrate. _{Then, the number average molecular weight (M n} ) and the molecular weight distribution index (M _w / M _n ) of the free polymer were measured by the size exclusion chromatography method, and the number average molecular weight (M n) of the polymer chain and the number average molecular weight (M _n ) of the polymer chain were measured as they were. A method used as a molecular weight distribution index (M _w / M _n ) can also be adopted. It has been confirmed that the number average molecular weight (M _n ) and the molecular weight distribution index (M _w / M _n ) are almost equal between the polymer chain fixed to the substrate and the free polymer produced during the polymerization reaction.

A method for measuring the molecular weight using a free polymer will be specifically described. When a polymer chain is synthesized by surface-initiated living radical polymerization, when a release initiator is added to the polymerization solution, a free polymer having a molecular weight and a molecular weight distribution equivalent to that of the polymer chain constituting the polymer chain aggregate can be obtained. it can. _{The number average molecular weight (M n} ) and the molecular weight distribution index (M _w / M _n ) are determined by analyzing this free polymer by size exclusion chromatography.

The analysis by the size exclusion chromatography method is a calibration method using a standard sample of the same kind and monodisperse with a known molecular weight, and an absolute molecular weight evaluation using a multi-angle light scattering detector. In the present specification, in the examples of the present specification, the values of the number average molecular weight (Mn) and the weight average molecular weight (Mw) are appropriately calculated using a multi-angle light scattering detector and molecular weight calibration curves of various standard samples. It is shown by the absolute value. Examples of the standard sample include a polystyrene standard sample, a polymethylmethacrylate standard sample, and a polyethylene glycol standard sample.

The density of the polymer chains on the surface of the base material ^{is preferably 0.01 chains / nm 2} or more, more preferably 0.05 chains / nm ² or more, and 0.1 chains / nm ² or more. It is more preferable, and 0.2 chain / nm ² or more is particularly preferable. The upper limit is not particularly limited, but may be 1.0 chain / nm ² or less, and may be 0.9 chain / nm ² or less.

The density of the polymer chains can be obtained by measuring the graft amount (W) per unit area and the number average molecular weight (M _n ) of the polymer chain aggregates and using the following formula.
Polymer chain density (chain / nm ² ) = W (g / nm ² ) / M _n × (Avogadro's number)
In the formula, W represents the graft amount per unit area, and _Mn represents the number average molecular weight of the polymer chain aggregate.
When the substrate is a flat substrate such as a silicon wafer, the graft amount (W) per unit area is the thickness in the dry state by the ellipsometry method, that is, the thickness of the polymer chain aggregate layer in the dry state. It can be obtained by measuring and calculating the graft amount (W) per unit area using the density of the bulk film.
The method for measuring the number average molecular weight (M _n ) of the polymer chain aggregate can be measured by the method described above.

The surface occupancy of the polymer chains on the surface of the base material (polymer cross-sectional area x polymer chain density x 100) is preferably 1% or more, more preferably 5% or more, and 10% or more. It is more preferable to have. The surface occupancy rate means the ratio of the graft points (first structural unit) to the surface of the base material, and is 100% in the dense packing. The method for calculating the density of the polymer chains can be measured by the method described above. The cross-sectional area of the polymer can be determined using the repeating unit length and the bulk density of the polymer in the stretched form of the polymer.

[B] Polymer having a bottle brush structure Next, a polymer having a bottle brush structure will be described.
The bottle brush structure is a branched polymer structure in which a plurality of side chains are branched from the main chain to form a bottle brush-like shape as a whole. In the polymer having a bottle brush structure, the main chain constitutes a base material and the side chains form a polymer chain aggregate, and further, the polymer having a bottle brush structure is fixed to the base material as a carrier. May be good. Examples of the carrier include those described above. Further, in this case, both the polymer having the bottle brush structure and the polymer brush may be fixed to the carrier which is the base material. In that case, the polymer brush is preferably a concentrated polymer brush.

A polymer having a bottle brush structure can also be obtained by the graft polymerization method. This graft polymerization is carried out from a Grafting-to method in which a pre-synthesized reactive side chain (graft chain) is bonded to a stem polymer which is a main chain, and a polymerization initiating group of a macroinitiator (a stem polymer in which a polymerization initiating group is introduced). It can be carried out by using the Grafting-from method for growing a side chain (graft chain) and the Grafting-throwh method for polymerizing a macromonomer (a polymer having a polymerizable functional group at the end of a side chain constituent polymer). In addition, living anionic polymerization, ring-opening metathesis polymerization (ROMP), or a highly versatile living radical polymerization method (LRP) can be used for the synthesis of these side chains and stem polymers. A preferable example of the polymer having a bottle brush structure is a compound represented by the formula (11).

In the formula (11), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ represents a substituent, preferably an alkyl group having 1 to 10 carbon atoms. R ⁴ and R ⁵ represent a terminal group composed of an atom or an atomic group, and examples thereof include a hydrogen atom, a halogen, and a functional group derived from a polymerization initiator. X represents O or NH, Y represents a divalent organic group, n represents an integer of 10 or more, and Polymer A represents a polymer chain. In the compound represented by the formula (11), the repeating structure of the structural unit enclosed by n corresponds to the main chain of the bottle brush structure, and Polymer A corresponds to the side chain of the bottle brush structure.

As the organic group represented by Y, an alkylene group having 1 to 10 carbon atoms, an oxyalkylene group (RO) having 1 to 5 carbon atoms (R represents an alkylene group having 1 to 5 carbon atoms), and a plurality of these oxyalkylene groups are linked. Divalent organic consisting of at least two combinations of these organic groups (alkylene groups having 1 to 10 carbon atoms, oxyalkylene groups having 1 to 5 carbon atoms and linked structures of oxyalkylene groups). The groups can be mentioned. Here, the alkylene group and the alkylene group of the oxyalkylene group may be linear or branched, and may have a cyclic structure. Specific examples of the alkylene group include an ethylene group, a propylene group, a butylene group, and a cyclohexylene group. The alkylene group and the alkylene group of the oxyalkylene group may be substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a heteroaryl group having 3 to 40 carbon atoms, and these substituents are further substituted with a substituent. May be good. For the description of Polymer A, a preferable range, and specific examples, the description in the above-mentioned (Polymer chain) column of the polymer chain can be referred to. Polymer A may be the same as or different from each other among the constituent units of the main chain.

For a polymer having a bottle brush structure, when the main chain is the central axis, the side chain (graft chain) is extended linearly from the central axis, and the surface including the tip (virtual outer peripheral portion) is assumed, the polymer of the polymer The outer shape can be regarded as a cylinder whose side surface is the surface including its tip. In a polymer having such an outer shape, the longer the length of the side chain (graft chain), the lower the density of the side chain (graft chain) on the side chain, and the higher the degree of freedom in the structure of the side chain (graft chain). Become. As a result, the side chain (graft chain) can be freely folded.

In a polymer having a bottle brush structure, the surface occupancy (σ ^* ) of the side chain is represented by the following formula (1).

In the formula (1), σ represents the density of the side chain of the virtual outer peripheral portion, which is obtained by the following formula (2), and the volume (V ₀ [nm ³ ]) per repeating unit of the side chain portion is It is calculated by the following formula (3).

In equation (2), α represents the length of the repeating unit of the main chain and the side chain portion.

Since the side chain density (σ) obtained by the formula (2) indicates the number of side chains per unit area on the side chain of the polymer, the side chain surface occupancy (σ ^* ) obtained by the formula (1) is , A value representing the proportion of the side chain tip on the side chain of the polymer in a state where the side chain is extended in a straight line in the vertical direction from the main chain. The surface occupancy (σ ^* ) of the side chain shows a value of 0 to 100%, and the larger the value, the larger the ratio occupied by the tip of the side chain on the side chain of the polymer, and the degree of freedom of the side chain is limited. become. That is, the surface occupancy of the side chain is a numerical value that reflects the degree of freedom of the side chain, and the ^{higher the surface occupancy (σ *} ) of the side chain, the more the structural freedom of the side chain is limited. As a result, it is presumed that the side chain can be maintained in a state of extending substantially perpendicular to the main chain, and exhibits properties peculiar to the structure.

The surface occupancy of the side chain of the polymer having a bottle brush structure is preferably 1% or more, more preferably 5% or more, and further preferably 10% or more.

The density of the side chains of the polymer having a bottle brush structure ^{is preferably 0.01 chain / nm 2} or more, more preferably 0.05 chain / nm ² or more, and 0.1 chain / nm ² or more. Is more preferable, and 0.2 chain / nm ² or more is particularly preferable. The upper limit is not particularly limited, but may be 1.0 chain / nm ² or less, and may be 0.9 chain / nm ² or less.

The number average molecular weight of the polymer having a bottle brush structure is preferably 1,000 to 10,000,000, more preferably 1,000 to 1,000,000, and 5,000 to 500,000. Is more preferable.

The molecular weight distribution index (PDI = M _w / M _n ) of the polymer having a bottle brush structure is preferably 1.0 to 2.0, more preferably 1.0 to 1.5. When the molecular weight distribution index is within the above range, the effect of maintaining a high-density state up to the outermost surface of the polymer chains constituting the polymer chain aggregate can be expected.

[Liquid substance]
The layer containing the polymer chain aggregate of the member of the present invention holds a liquid substance.

Examples of the liquid substance include water, ionic liquid, fluorine-based solvent, oil (hydrocarbon-based oil, silicone oil, etc.), and preferably at least one selected from water and ionic liquid. The liquid substance may be a hydrophilic liquid substance or a hydrophobic liquid substance. Examples of the hydrophilic liquid substance include water and a hydrophilic ionic liquid. Examples of the hydrophobic liquid substance include hydrophobic ionic liquids, fluorine-based solvents, and oils. The liquid substance may be composed of only one kind of liquid substance, or may be a mixture of two or more kinds of liquid substances. The liquid substance may contain additives.

An ionic liquid is a low melting point salt having ionic conductivity, which is also called an ionic liquid or a room temperature molten salt. Most ionic liquids have relatively low melting point properties obtained by combining organic onium ions as cations with organic or inorganic anions as anions. The melting point of the ionic liquid is usually 100 ° C. or lower, preferably room temperature (25 ° C.) or lower. The melting point of the ionic liquid can be measured by a differential scanning calorimeter (DSC) or the like.

As the ionic liquid, a compound represented by the following formula (20) can be used. The melting point of this ionic liquid is preferably 50 ° C. or lower, more preferably 25 ° C. or lower.

In formula (20), R ²¹ , R ²² , R ²³ and R ²⁴ are each independently an alkyl group having 1 to 5 carbon atoms or an alkoxyalkyl group represented by _{R'-O- (CH 2} ) _n-. , R'represents a methyl group or an ethyl group, and n is an integer of 1 to 4. R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different from each other. Further, ^{any two of R 21} , R ²² , R ²³ and R ²⁴ may be bonded to each other to form an annular structure. However, ^{at least one of R 21} , R ²² , R ²³ and R ²⁴ is an alkoxyalkyl group. X ²¹ represents a nitrogen atom or a phosphorus atom, and Y represents a monovalent anion.

Examples ^{of the alkyl group having 1 to 5 carbon atoms in R 21} , R ²² , R ²³ and R ²⁴ include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, an n-butyl group and an n-pentyl group. Be done.
In R ²¹ , R ²² , R ²³ and R ²⁴ , the alkoxyalkyl group represented by R'-O- (CH ₂ ) _n- includes a methoxymethyl group or an ethoxymethyl group, a 2-methoxyethyl group or 2- An ethoxyethyl group, a 3-methoxypropyl group or a 3-ethoxypropyl group, a 4-methoxybutyl group or a 4-ethoxybutyl group and the like are preferable.
As ^{a compound in which any two of R 21} , R ²² , R ²³ and R ²⁴ are bonded to each other to form a cyclic structure, ^{when a nitrogen atom is adopted for X 21} , an aziridine ring, an azetidine ring and a pyrrolidine are used. A quaternary ammonium salt having a ring, a piperidine ring or the like is preferable, and ^{when a phosphorus atom is adopted for X 21} , a quaternary phosphonium salt having a pentamethylenephosphine (phosphorinan) ring or the like is preferable. The quaternary ammonium salt preferably has at least one 2-methoxyethyl group in which R'is a methyl group and n is 2 as a substituent.
The monovalent anion in _{^{Y, BF 4 -, PF 6}} -, AsF 6 -, SbF 6 -, AlCl 4 -, NbF 6 -, HSO 4 -, ClO 4 -, CH 3 SO 3 -, CF 3 SO _{^{3 -, CF 3 CO 2 -}} , (CF 3 SO 2) 2 N -, Cl -, Br -, I - , and the _{^{like, BF 4 -, PF 6 -}} , (CF 3 SO 2) 2 N -, CF ₃ SO ₃ ^-, or _CF 3 CO ₂ ^- is suitably a.

As the ionic liquid, R ²¹ of the formula (20) is a methyl group, R ²³ and R ²⁴ are ethyl groups, and R ²⁴ is an alkoxyalkyl group represented by R'-O- (CH ₂ ) _n-. A compound having a structure is preferably used.

Among the compounds represented by the formula (20), the following compounds can be mentioned as specific examples of the quaternary ammonium salt and the quaternary phosphonium salt that are preferably used.

Further, as the ionic liquid, an ionic liquid containing imidazolium ions or an ionic liquid containing aromatic cations can also be used.

The method for retaining the liquid substance in the layer containing the polymer chain aggregate is not particularly limited. For example, a method in which a liquid substance is applied to the surface of a layer containing a polymer chain aggregate and then allowed to stand and held, or a method in which a base material on which a layer containing a polymer chain aggregate is formed is immersed in the liquid substance. And so on. In addition, the polymer chain aggregate may take in moisture in the atmosphere and retain water, which is a liquid substance, in the layer containing the polymer chain aggregate.

[Characteristics of members]
The contact angle of the surface of the member of the present invention with water at 25 ° C. is preferably 10 ° or more, more preferably 20 ° or more, further preferably 45 ° or more, and 48 ° or more. Is even more preferable, and 48 to 80 ° is particularly preferable. When the contact angle is within the above range, a more excellent effect of suppressing water droplet adhesion, an effect of suppressing icing, and an effect of suppressing ice nucleation can be obtained. In the present specification, the value of the contact angle of the surface of the member with respect to water is a value obtained by measuring the contact angle of water on the surface of the member 1 second after applying 1 μL of water to the surface of the member.

[Shape of member]
The shape of the member of the present invention is not particularly limited. Examples include tube, sheet, fibrous, strip, film, plate, foil, film, pellet, powder, and particle.

[Applicable form of member]
The members of the present invention can be applied to various articles. For example, window glass, vehicle glass, mirrors, heat exchangers, pipes, containers and the like can be mentioned.

The present invention will be described in more detail with reference to examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Test Example 1]
(Example 1)
The sample pan (Tzero Low-Mass Pan, material: aluminum, manufactured by TA Instruments) was ultrasonically cleaned in acetone for 30 minutes, chloroform for 30 minutes, and 2-propanol for 30 minutes, respectively, and then the sample pan. Both sides of the surface were irradiated with UV ozone for 10 minutes. Next, this sample pan was _{immersed in an ethanol solution of NH 3} 0.24 mol / L and tetraethoxysilane 0.03 mol / L for 24 hours, and the surface of the sample pan was coated with silica. Next, the silica-coated sample pan was ultrasonically washed in ethanol for 30 minutes, and then (2-bromo-2-methyl) propionyloxypropyltrimethoxysilane (BPM) / ethanol / aqueous ammonia = 1/89. It was immersed in a mixed solution of 1/10 (mass ratio) and immersed for 24 hours to introduce a polymerization initiating group into a sample pan. Next, after introducing the polymerization initiating group, UV ozone was irradiated only on the back surface of the sample pan for 10 minutes to remove the polymerization initiating group only on the back surface of the sample pan. Next, methoxypoly (ethylene glycol) methacrylate (manufactured by Aldrich, code 447943, number average molecular weight = 500) (hereinafter, PEGMA), ethyl2-bromo-2-methylpropionate (hereinafter, EBIB), and bromide. A mixture (PEGMA / EBIB) of monocopper (hereinafter, CuBr (I), cupric bromide (hereinafter, CuBr (II)), and 4,4'-dinonyl-2,2'-bipyridine (hereinafter, diNbip)). / CuBr (I) / CuBr (II) / diNbip = 200,000 / 1/648/72/1440 (molar ratio)) in 50 parts by mass and 50 parts by mass of anisole in a fluororesin container. A sample pan into which the initiator group was introduced was placed. The container was sealed and covered with an aluminum bag, and the polymerization reaction was carried out at 400 MPa and 60 ° C. for 4 hours in a high-pressure reactor. After the polymerization reaction was completed, the sample pan was removed from the container. It was taken out and washed with tetrahydrofuran using a shaking device. Then, by drying, a brush-like polymer chain aggregate (polymer brush layer) composed of a plurality of polymer chains was formed on the inner surface of the sample pan. A test piece of Example 1 was obtained.

The thickness of the polymer brush layer formed on the inner surface of the sample pan is 630 nm, the number average molecular weight is 2.88 million, the molecular weight distribution index (PDI) is 1.60, the polymer polymerization rate is 6%, and the density of polymer chains is 0. The surface occupancy of the polymer chain was 14% at 15 chains / nm ^2. The film thickness of the polymer brush layer was measured by a spectroscopic ellipsometry method. The number average molecular weight and the molecular weight distribution index of the polymer brush layer were calculated by gel permeation chromatography using dimethylformamide containing 10 mM lithium bromide as a developing solvent and a multi-angle light scattering detector as a detector. The polymer polymerization rate was ^{measured by 1 1} H-NMR.

(Comparative Example 1)
The sample pan (Tzero Low-Mass Pan, material: aluminum, manufactured by TA Instruments) was ultrasonically cleaned in acetone for 30 minutes, chloroform for 30 minutes, and 2-propanol for 30 minutes, respectively, and then the sample pan. Both sides of the surface were irradiated with UV ozone for 10 minutes. This sample pan was used as the test body of Comparative Example 1.

(Comparative Example 2)
The sample pan (Tzero Low-Mass Pan, material: aluminum, manufactured by TA Instruments) was ultrasonically cleaned in acetone for 30 minutes, chloroform for 30 minutes, and 2-propanol for 30 minutes, respectively, and then the sample pan. Both sides of the surface were irradiated with UV ozone for 10 minutes. Next, this sample pan was _{immersed in an ethanol solution of NH 3} 0.24 mol / L and tetraethoxysilane 0.03 mol / L for 24 hours, and the surface of the sample pan was coated with silica. This silica-coated sample pan was used as the test piece of Comparative Example 2.

[Evaluation]
Distilled water was sprayed onto each of the test specimens of Example 1, Comparative Example 1, and Comparative Example 2 to add a small amount of water, and then a lid (Tzero Hermetic Lid, manufactured by TA Instruments) was put on the test piece to seal the test piece, and the Discovery DSC 2500 Using a differential scanning calorimeter (manufactured by TA Instruments), cool from 25 ° C to -90 ° C at a cooling rate of 5 ° C / min, and then raise to 25 ° C at a heating rate of 2 ° C / min. Then, the differential scanning calorimetry was performed, and the change in heat flow due to the heat absorption and heat generation of water was detected. When the test piece of Example 1 was used, an endothermic peak was observed near −40 ° C. when the temperature was raised, but when the test pieces of Comparative Examples 1 and 2 were used, an endothermic peak was observed only around 0 ° C. It was seen. From the endothermic peak at the time of temperature rise and the heat of fusion ΔH obtained from the endothermic peak area, free water (water melted at 0 ° C), bound water (water melted near -40 ° C), antifreeze water (even at -90 ° C). The weights of the water classified as (non-frozen water) were calculated. The results are shown in the table below. The weight of each classified water was calculated from the following formula.
Weight of each classified water = {heat of fusion of each classified water ΔH (J / g) /333.5} × weight of added water

As shown in the above table, it was found that Test Example 1-1 and Test Example 1-2 using the test body of Example 1 had bound water and antifreeze water that did not freeze even at a temperature lower than 0 ° C. .. From this result, it can be understood that the test body of Example 1 is less likely to freeze water and is excellent in icing suppression property and ice nucleation suppression property.

In Test Example 1-2, a hole was made in the lid and dried at 150 ° C. for 30 minutes and at 200 ° C. for 30 minutes. Since there was no change in weight after drying at 200 ° C. for 30 minutes, it was judged that the product was completely dried. From the change in weight of the test piece before and after drying, the water content contained in the test piece of Test Example 1-2 was 0.0167 mg. In Test Example 1-2, since the amount of water added was 0.0150 mg, it is presumed that in Test Example 1-2, the polymer brush layer of the test body absorbed about 0.0017 mg of water in the atmosphere. To.

[Test Example 2]
(Example 11)
A brush-like polymer chain aggregate (polymer brush layer) composed of a plurality of polymer chains was formed on the surface of the silicon wafer in the same manner as in Example 1 except that a silicon wafer was used instead of the sample pan. Specimens of Example 11 were obtained. The test piece was allowed to stand in the air for 24 hours or more to allow the polymer brush layer to absorb water, and then 1 μL of water at 25 ° C. was plucked on the surface of the polymer brush layer of the test piece. The contact angle of was measured. The contact angle of the test piece of Example 11 with water at 25 ° C. was 45.3 °.

(Example 12)
A brush-like polymer chain aggregate (polymer brush layer) composed of a plurality of polymer chains was formed at 380 nm on the surface of the silicon wafer in the same manner as in Example 1 except that a silicon wafer was used instead of the sample pan. Specimens of Example 12 were obtained. The test piece was allowed to stand in the air for 24 hours or more to allow the polymer brush layer to absorb water, and then 1 μL of water at 25 ° C. was plucked on the surface of the polymer brush layer of the test piece. The contact angle of was measured. The contact angle of the test piece of Example 12 with water at 25 ° C. was 49.4 °.

(Example 13)
A brush-like polymer chain aggregate (polymer brush layer) composed of a plurality of polymer chains was formed at 750 nm on the surface of the silicon wafer in the same manner as in Example 1 except that a silicon wafer was used instead of the sample pan. Specimens of Example 13 were obtained. The test piece was allowed to stand in the air for 24 hours or more to allow the polymer brush layer to absorb water, and then 1 μL of water at 25 ° C. was plucked on the surface of the polymer brush layer of the test piece. The contact angle of was measured. The contact angle of the test body of Example 13 with water at 25 ° C. was 61.3 °.

(Example 14)
A brush-like polymer chain aggregate (polymer brush layer) composed of a plurality of polymer chains was formed at 1070 nm on the surface of the silicon wafer in the same manner as in Example 1 except that a silicon wafer was used instead of the sample pan. Specimens of Example 14 were obtained. The test piece was allowed to stand in the air for 24 hours or more to allow the polymer brush layer to absorb water, and then 1 μL of water at 25 ° C. was plucked on the surface of the polymer brush layer of the test piece. The contact angle of was measured. The contact angle of the test piece of Example 14 with water at 25 ° C. was 64.7 °.

(Example 15)
A brush-like polymer chain aggregate (polymer brush layer) composed of a plurality of polymer chains was formed at 1250 nm on the surface of the silicon wafer in the same manner as in Example 1 except that a silicon wafer was used instead of the sample pan. Specimens of Example 15 were obtained. The test piece was allowed to stand in the air for 24 hours or more to allow the polymer brush layer to absorb water, and then 1 μL of water at 25 ° C. was plucked on the surface of the polymer brush layer of the test piece. The contact angle of was measured. The contact angle of the test piece of Example 15 with water at 25 ° C. was 72.4 °.

(Comparative Example 11)
The silicon wafer was ultrasonically cleaned in acetone for 30 minutes, in chloroform for 30 minutes and in 2-propanol for 30 minutes, and then both sides of the silicon wafer were irradiated with UV ozone for 10 minutes. This silicon wafer was used as a test body of Comparative Example 11.

[Evaluation]
After each test piece was allowed to stand in a freezer at a temperature of −25 ° C. for 2 hours, the test piece was moved to an environment having a temperature of 20 ° C. and a relative humidity of 56%, and the state of the surface of each test piece was confirmed 1 minute later.

The test bodies of Examples 11 to 15 were less likely to cause dew condensation than the test bodies of Comparative Example 11. Further, in Examples 14 and 15, there was no fogging, and dew condensation could be suppressed more effectively. Moreover, when the examples 11 to 13 were compared, the cloudiness of Examples 12 and 13 was less than that of Example 11.

Claims (11)

1. It has a layer containing a brush-like polymer chain aggregate composed of a plurality of polymer chains fixed to a base material, and the layer containing the polymer chain aggregate holds a liquid substance.
   A member for anti-fog, suppression of water droplet adhesion, suppression of icing or suppression of ice nucleation.
2. The member according to claim 1, wherein the liquid substance is held in a layer containing the polymer chain aggregate and keeps a liquid state even at a temperature lower than the freezing point.
3. The member according to claim 1 or 2, wherein the liquid substance is water or an ionic liquid.
4. The member according to any one of claims 1 to 3, wherein the base material is a carrier made of a substance different from the polymer chain aggregate.
5. The member according to claim 4, wherein only one end of the polymer chains constituting the polymer chain aggregate is fixed to the base material.
6. The member according to claim 4, wherein both ends of the polymer chains constituting the polymer chain aggregate are fixed to the base material.
7. The member according to any one of claims 4 to 6, wherein the density of the polymer chains on the surface of the base material is 0.01 chains / nm ^{2 or more.}
8. The base material is a polymer chain
   The member according to any one of claims 1 to 3, wherein the plurality of polymer chains are bonded to the polymer chain as the base material as side chains to form a polymer having a bottle brush structure.
9. The member according to claim 8, wherein the polymer having a bottle brush structure has a side chain density of 0.01 chain / nm ^{2 or more.}
10. The member according to any one of claims 1 to 9, wherein the film thickness of the layer containing the polymer chain aggregate is 350 nm or more.
11. The member according to any one of claims 1 to 10, wherein the contact angle of the surface of the member with water at 25 ° C. is 10 ° or more.