JP2022157406A - Virus inactivation structure - Google Patents

Abstract

To provide a virus inactivation structure that has a high virus inactivation function and can retain such a high virus inactivation function for a long time.SOLUTION: The present invention discloses a virus inactivation structure having a virus inactivation function, comprising a polymer brush structure that comprises a plurality of polymer chains each comprising a functional group selected from an ionic group, a nonionic hydrophilic group and an electron-donating group.SELECTED DRAWING: None

Description

Patent Law Article 30, Paragraph 2 application filed December 24, 2020, https://www. amed. go. jp/news/topics/covid19_06. html [Publications, etc.] January 4, 2021, https://www. tsuruoka-nct. ac. jp/wp-content/uploads/2020/12/20210104-r. pdf [Publications, etc.] January 9, 3rd year of Reiwa, Shonai Nippo January 9, 3rd year of Reiwa, page 1

TECHNICAL FIELD The present invention relates to a virus-inactivating structure having a high virus-inactivating function and capable of maintaining the high virus-inactivating function over a long period of time.

Many viral diseases such as influenza, measles, and chickenpox are easily transmitted by viruses attached to familiar objects, droplet infection, droplet nuclear infection, and the like. Therefore, countermeasures against viral infections are a major issue in modern society. As an attempt to combat virus infection, for example, Patent Document 1 proposes a compound having a virus-inactivating action.

On the other hand, the global epidemic of the new coronavirus (COVID-19) has become a major problem that is pressing for changes in social life. In addition, from the viewpoint of stable sedation, a material that has a high virus-inactivating function and that can maintain the high virus-inactivating function over a long period of time is eagerly desired.

JP 2020-128342 A

The present invention has been made in view of such circumstances, and its object is to provide a virus-inactivating structure that has a high virus-inactivating function and that can sustain the high virus-inactivating function over a long period of time. .

As a result of intensive studies to achieve the above object, the present inventors have found that a polymer brush structure containing a plurality of polymer chains having functional groups selected from ionic groups, nonionic hydrophilic groups and electron donating groups, The inventors have found that they have a high virus-inactivating function and that the high virus-inactivating function can be maintained over a long period of time, and have completed the present invention.

That is, the present invention relates to the following matters.
[1] A virus-inactivating structure having a virus-inactivating function, comprising a polymer brush structure containing a plurality of polymer chains having functional groups selected from ionic groups, nonionic hydrophilic groups and electron-donating groups.
[2] The virus-inactivating structure according to [1], wherein the plurality of polymer chains are water-soluble.
[3] The virus-inactivating structure according to [1] or [2], wherein the plurality of polymer chains are covalently immobilized on a substrate to form a polymer brush structure.
[4] The ratio (T _b /L _p ) of the thickness T _b of the polymer brush structure to the average molecular chain length L _p of the polymer chains constituting the polymer brush structure is 0.001 to 0.6. The virus-inactivating structure according to [3].
[5] The virus-inactivating structure according to [3] or [4], wherein the substrate is fiber, single fiber, twisted yarn, woven fabric, non-woven fabric, cut fiber, hollow fiber, glass, metal, or a processed product thereof. .
[6] At least one end of the plurality of polymer chains is present in the base polymer, and at least a portion thereof is exposed from the base polymer, thereby forming a polymer brush structure. A virus-inactivating structure according to [1] or [2].
[7] The plurality of polymer chains are polymer graft chains branched from a polymer chain serving as a main chain, thereby forming a bottle brush-like polymer brush structure [1] or [2] A virus-inactivating structure as described in .
[8] The virus-inactivating structure according to any one of [1] to [7], wherein the polymer brush structure has an ionic conductivity of 5.0×10 ⁻¹ S/m or less.
[9] The virus-inactivating structure according to any one of [1] to [8], wherein the plurality of polymer chains have an ammonium group.

According to the present invention, it is possible to provide a virus-inactivating structure that has a high virus-inactivating function and that can maintain the high virus-inactivating function over a long period of time.

FIG. 1 is a diagram showing a virus inactivation structure according to a first embodiment of the present invention. FIG. 2 shows a virus inactivation structure according to a second embodiment of the invention. FIG. 3 shows a virus inactivation structure according to a third embodiment of the invention.

The virus-inactivating structure of the present invention comprises a polymer brush structure containing a plurality of polymer chains having specific functional groups selected from ionic groups, non-ionic hydrophilic groups and electron-donating groups, and has a virus-inactivating function. have.
As a result of intensive studies by the present inventors, it was found that a polymer brush structure containing a plurality of polymer chains having specific functional groups selected from ionic groups, nonionic hydrophilic groups, and electron-donating groups was highly resistant to viruses. The present inventors have completed the present invention based on the discovery that it has activation and that such virus-inactivating function is maintained over a long period of time. In particular, the present inventors have found for the first time that such effects are unique to the polymer brush structure. Here, the polymer brush structure may be any structure provided with a plurality of polymer chains physically or chemically fixed to some kind of substrate, and as long as it has such a structure, its shape and the like are not particularly limited. not something.

<First embodiment>
First, a first embodiment of the present invention will be described.
FIG. 1 is a diagram showing a virus inactivation structure according to a first embodiment of the present invention. As shown in FIG. 1, the virus inactivating structure according to the first embodiment comprises a substrate 10 and a polymer brush layer 20 formed on the substrate 10. As shown in FIG.

The substrate 10 is not particularly limited, and includes a wide range of materials such as fibers, single fibers, twisted yarns, woven fabrics, non-woven fabrics, cut fibers, hollow fibers, glass, metals, and processed products thereof. Particles such as silica and carbon black may also be used. In particular, according to the present invention, by using an arbitrary material and an arbitrary shape as the substrate 10 and forming the polymer brush layer 20 on the surface thereof, for an arbitrary material having an arbitrary shape, A virus inactivating effect can be imparted by the polymer brush layer 20 .

The polymer brush layer 20 is a layer containing a plurality of polymer chains covalently fixed on the substrate 10 as a substrate. It is formed by a polymer chain having a specific functional group (hereinafter referred to as "specific functional group" as appropriate) selected from a hydrophilic group and an electron donating group.

In the present invention, the reason why the polymer brush layer 20 exhibits the virus inactivating action is not necessarily clear, but the following reasons are conceivable. That is, when a virus adheres to the surface of the polymer brush layer 20, a plurality of polymer chains having specific functional groups that constitute the polymer brush layer 20 fuse with the envelope that constitutes the virus ( pseudo-infection), causing envelope cleavage. It is believed that the RNA inside the virus is expelled to the outside due to the high osmotic pressure of the polymer chain having the specific functional group, thereby inactivating the virus.

In the present invention, the polymer brush layer 20 is composed of a plurality of polymer chains having specific functional groups. Since it is composed of a plurality of polymer chains, it exhibits high osmotic pressure, and it can be said that it exhibits a high virus-inactivating function. In addition, since the polymer brush layer 20 has a structure composed of a plurality of polymer chains, such a high virus inactivation function can be stably exhibited without accompanying structural changes. Therefore, it can be said that the high virus inactivation function is sustainable over a long period of time.

Therefore, according to the present invention, a high inactivation effect can be obtained for various viruses, particularly enveloped viruses. As described above, in the present invention, a plurality of polymer chains having specific functional groups, which constitute the polymer brush layer 20, fuse (pseudo-infect) with the envelope constituting the virus to cleave the envelope. , and the envelope that constitutes the virus is generally composed of a phospholipid bilayer membrane. On the other hand, fungi such as bacteria have cell membranes composed of polysaccharides, etc. In this respect, viruses and fungi such as bacteria are completely different. They are completely different from viruses. In particular, those exhibiting a bactericidal or antibacterial effect generally destroy cell membranes composed of polysaccharides (that is, act on polysaccharides), whereas in the present invention, phospholipid dihydrogenase Since it is thought to have the effect of fusing with and cleaving the envelope composed of a heavy membrane (that is, acting on the phospholipid bilayer membrane), its mechanism of action and required properties are bactericidal or antibacterial. It is considered that it is different from the one showing the action.

A plurality of polymer chains constituting the polymer brush layer 20 have functional groups selected from ionic groups, nonionic hydrophilic groups and electron donating groups as specific functional groups.

The ionic group is not particularly limited, and may be either a cationic functional group or an anionic functional group. Examples include acid groups, carboxylic acid groups, acrylic acid groups, methacrylic acid groups or groups that are salts thereof, and salts such as hydroxyl groups and thiol groups.

When the ionic group is a cationic functional group, it usually forms a salt structure together with a counter anion. , forming a salt structure. Counter anions include, but are not limited to, 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. Examples of counter cations include, but are not limited to, alkali metal ions such as Na ⁺ , K ⁺ and Li ⁺ ; alkaline earth metal ions such as Ca ²⁺ and Mg ²⁺ ; organic cations such as ammonium ions and alkylammonium ions; mentioned.

Examples of nonionic hydrophilic groups include, but are not particularly limited to, hydroxyl groups, amide groups, amino groups, ether bonds, thiol groups, and the like.

The electron-donating group may be a group exhibiting electron-donating properties that does not correspond to the above-mentioned ionic groups and nonionic hydrophilic groups. Examples include nitrogen, oxygen, sulfur, silicon and phosphorus atoms. containing groups, specific examples of which include a hydroxy group, an amino group, a methoxy group, a sulfide group, and the like.

Among the above-mentioned specific functional groups, ionic groups and nonionic hydrophilic groups are preferable from the viewpoint of having higher affinity for the envelope that constitutes the virus and, therefore, exhibiting a higher virus inactivating function. More preferred are cationic functional groups, and more preferred are ammonium groups. The plurality of polymer chains forming the polymer brush layer 20 may contain only one type of specific functional group, or may contain two or more types of specific functional groups.

Moreover, it is preferable that the plurality of polymer chains constituting the polymer brush layer 20 be composed of a water-soluble polymer. In particular, when the polymer brush layer 20 contains a small amount of water, or when the polymer brush layer 20 is wet with water (a layer that retains water), virus attachment From the standpoint of high efficiency, and further from the standpoint of achieving highly efficient virus inactivation, the plurality of polymer chains constituting the polymer brush layer 20 should be composed of water-soluble polymers. is preferred. In the present invention, when exhibiting water solubility in any of the pH range of 1 to 12 (for example, when 1% by weight of a polymer is dispersed in water, the absorbance is 0.3 or less). ), it can be determined that the polymer is water-soluble.

The polymer brush layer 20 can be formed, for example, by covalently fixing a plurality of polymer chains on the substrate 10. More specifically, the surface of the substrate 10 is subjected to surface-initiated living radical polymerization. It can be formed by introducing a polymer chain by a method.

In the surface-initiated living radical polymerization method, a polymer chain (polymer graft chain), and for example, the methods described in JP-A-2009-59659 and JP-A-2010-218984 can be applied.

〔上記一般式（１）中、ｍは、１以上１０以下の整数を示す。ｎは、１以上５以下の整数を示す。Ｒ^１は、水素原子、または炭素数１～３のアルキル基を示す。Ｒ^２、Ｒ^３、Ｒ^４は、炭素数１～５のアルキル基を示す。Ｒ^２、Ｒ^３、Ｒ^４は、酸素原子、硫黄原子、フッ素原子から選ばれる１種以上のヘテロ原子を含んでいてもよく、Ｒ^２、Ｒ^３、Ｒ^４は、２つ以上が連結して環状構造であってもよい。また、Ｚ^－は一価のアニオンを示す。〕 The monomer for forming the polymer chain is not particularly limited, and at least a monomer having the above-described specific functional group may be used. A monomer that can introduce an ammonium group into the chain is more preferable (that is, it is more preferable that a plurality of polymer chains constituting the polymer brush layer 20 have a structure having an ammonium group in a side chain). Examples of monomers having an ammonium group as a functional group include compounds represented by the following general formula (1). In addition, as a monomer having a specific functional group, one type may be used alone, or two or more types may be used in combination. Moreover, as a monomer for forming a polymer chain, a monomer copolymerizable with a monomer having a specific functional group (monomer having no specific functional group) may be used.

[In the above general formula (1), m represents an integer of 1 or more and 10 or less. n represents an integer of 1 or more and 5 or less. R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ² , R ³ and R ⁴ represent alkyl groups having 1 to 5 carbon atoms. R ² , R ³ and R ⁴ may contain one or more heteroatoms selected from an oxygen atom, a sulfur atom and a fluorine atom, and two or more of R ² , R ³ and R ⁴ are linked may have a cyclic structure. Also, Z ⁻ represents a monovalent anion. ]

The monovalent anion Z ⁻ in the general formula (1) is not particularly limited, and is BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , AlCl ₄ ⁻ , NbF ₆ ⁻ , HSO ₄ . Anions such as ⁻ , ClO ₄ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , CF ₃ CO ₂ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , Cl ⁻ , Br ⁻ and I ⁻ can be used. is BF ₄ ⁻ , PF ₆ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , CF ₃ SO ₃ ⁻ , or CF ₃ CO ₂ ⁻ .

〔上記一般式（２）～（９）中、ｎ、ｍ、Ｒ^１、Ｒ^２、Ｚ^－は、上記一般式（１）と同様である。〕 Among the compounds represented by the above general formula (1), the compounds represented by the following general formulas (2) to (9) can be particularly preferably used from the viewpoint of their high virus inactivation effect. In addition, these can be used individually by 1 type or in combination of 2 or more types.

[In the above general formulas (2) to (9), n, m, R ¹ , R ² and Z ^- are the same as in the above general formula (1). ]

Further, as the monomer used for forming the polymer chain, instead of the compound represented by the general formula (1), or together with the compound represented by the general formula (1), for example, (meth)acrylic Acid-based monomers, styrene-based monomers, monofunctional monomers having one addition-polymerizable double bond, hydrophobic monomers, hydrophilic monomers, monomers having a carboxyl group or a group that can be easily converted to a carboxyl group in the side chain etc. can also be used.

Specific examples of (meth)acrylic acid-based monomers include:
(meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 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 (meth)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-(meth)acryloxy)ethoxyethyl) ) phenylethoxy)piperidine, γ-(methacryloyloxypropyl)trimethoxysilane;
3-(3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octasiloxane-1-yl) Propyl (meth)acrylate, 3-(3,5,7,9,11,13,15-heptaisobutyl-pentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octa Siloxane-1-yl)propyl (meth)acrylate, 3-(3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1 ^{3,9.1 5,15} .1 ^7,13 ]octasiloxane-1-yl)propyl (meth)acrylate;
3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octasiloxane-1-yl) Propyl (meth)acrylate, 3-(3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octa Siloxane-1-yl)propyl (meth)acrylate, 3-[(3,5,7,9,11,13,15-heptaethylpentacyclo[ ^9.5.1.1 3,9.1 ^5,15 .1 ^7,13 ]octasiloxane-1-yloxy)dimethylsilyl]propyl (meth)acrylate;
3-[(3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octasiloxane-1-yloxy ) dimethylsilyl]propyl (meth)acrylate, 3-[(3,5,7,9,11,13,15-heptaisooctylpentacyclo[ ^9.5.1.1 3,9.1 ^5,15 . 1 ^7,13 ]octasiloxane-1-yloxy)dimethylsilyl]propyl (meth)acrylate;
3-[(3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octasiloxane-1-yloxy ) dimethylsilyl]propyl (meth)acrylate, 3-[(3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1 ^{3,9.1 5,15.1 7,13} ]octasiloxane-1-yloxy)dimethylsilyl]propyl (meth)acrylate;
(Meth)acrylic acid ethylene oxide adduct, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, trifluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate;
2-perfluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate; .

Specific examples of styrene-based monomers include
Styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, m-chloromethylstyrene, o-aminostyrene, p-styrenechlorosulfonic acid, styrenesulfonic acid and its salts, vinylphenylmethyldithio carbamate, 2-(2-bromopropionyloxy)styrene, 2-(2-bromoisobutyryloxy)styrene;
1-(2-((4-vinylphenyl)methoxy)-1-phenylethoxy)-2,2,6,6-tetramethylpiperidine, 1-(4-vinylphenyl)-3,5,7,9, 11,13,15-heptaethylpentacyclo[9.5.1.1 ^3,9 . ^15,15 . 1 ^7,13 ]octasiloxane, 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1 ^3,9 . ^15,15 . 1 ^7,13 ]octasiloxane;
1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1 ^3,9 . ^15,15 . 1 ^7,13 ]octasiloxane, 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1 ^3,9 . ^15,15 . 1 ^7,13 ]octasiloxane, 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1 ^3,9 . ^15,15 . 1 ^7,13 ]octasiloxane;
3-(3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octasiloxane-1-yl) Ethylstyrene, 3-(3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octasiloxane-1 -yl)ethylstyrene, 3-(3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl)ethylstyrene;
3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octasiloxane-1-yl) Ethylstyrene, 3-(3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octasiloxane-1 -yl)ethylstyrene, 3-(3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octa siloxane-1-yloxy)dimethylsilyl)ethylstyrene;
3-(3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octasiloxane-1-yloxy) dimethylsilyl)ethylstyrene, 3-(3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy)dimethylsilyl)ethylstyrene;
3-((3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octasiloxane-1-yloxy )dimethylsilyl)ethylstyrene, 3-((3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy)dimethylsilyl)ethylstyrene; and the like.

Specific examples of monofunctional monomers having one addition-polymerizable double bond include:
Fluorine-containing vinyl monomers (perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc.), silicon-containing vinyl monomers (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), maleic anhydride, maleic acid, maleic acid monoalkyl esters and dialkyls esters, fumaric acid, mono- and dialkyl esters of fumaric acid;
Maleimide-based monomers (maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc.);
Nitrile group-containing monomers (acrylonitrile, methacrylonitrile, etc.), amide group-containing monomers (acrylamide, methacrylamide, etc.), vinyl ester monomers (vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, etc.) ;
Olefins (ethylene, propylene, etc.), conjugated diene monomers (butadiene, isoprene, etc.), vinyl halides (vinyl chloride, etc.), vinylidene halides (vinylidene chloride, etc.), allyl halides (allyl chloride, etc.);
allyl alcohol, vinylpyrrolidone, vinylpyridine, N-vinylcarbazole, methylvinylketone, vinylisocyanate;
Further, the monofunctional monomer having one addition polymerizable double bond includes one polymerizable double bond in one molecule, and the main chain is styrene, (meth)acrylic acid ester, Macromonomers and the like derived from siloxanes and the like can also be used.

Specific examples of hydrophobic monomers include
Acrylic acid esters (alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, hexafluoroisopropyl acrylate; aryl acrylates such as phenyl acrylate; aryl alkyl acrylates such as benzyl acrylate; methoxymethyl acrylate, etc. alkoxyalkyl acrylate, etc.);
Methacrylic acid esters (alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, hexafluoroisopropyl methacrylate; aryl methacrylates such as phenyl methacrylate; arylalkyl methacrylates such as benzyl methacrylate; methoxymethyl methacrylate, etc. alkoxyalkyl methacrylate, etc.);
fumaric acid ester (dimethyl fumarate, diethyl fumarate, alkyl ester of fumaric acid such as diallyl fumarate, etc.), maleic acid ester (alkyl ester of maleic acid such as dimethyl maleate, diethyl maleate, diallyl maleate, etc.);
Itaconic acid esters (such as alkyl esters of itaconic acid), crotonic acid esters (such as alkyl esters of crotonic acid), methyl vinyl ether, ethoxyethyl vinyl ether, vinyl acetate, vinyl propionate, vinyl benzoate, styrene;
Alkyl styrene, vinyl chloride, vinyl methyl ketone, vinyl stearate, vinyl alkyl ether;

Specific examples of hydrophilic monomers include
hydroxy-substituted alkyl acrylates (2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,3-dihydroxypropyl acrylate, polyethoxyethyl acrylate, polyethoxypropyl acrylate, etc.);
hydroxy-substituted alkyl methacrylates (2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, polyethoxyethyl methacrylate, polyethoxypropyl methacrylate, etc.);
acrylamide, N-alkylacrylamide (N-methylacrylamide, N,N-dimethylacrylamide, etc.), N-alkylmethacrylamide (N-methylmethacrylamide, etc.);
polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, alkoxypolyethyleneglycol acrylate, alkoxypolyethyleneglycol methacrylate, phenoxypolyethyleneglycol acrylate, phenoxypolyethyleneglycol methacrylate, 2-glucosyloxyethyl methacrylate;
acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, methacrylamide, allyl alcohol, N-vinylpyrrolidone, N,N-dimethylaminoethyl acrylate;

Specific examples of monomers having a carboxyl group or a group that can be easily converted to a carboxyl base in the side chain include:
1-methoxyethyl acrylate, 1-ethoxyethyl acrylate, 1-propoxyethyl acrylate, 1-(1-methylethoxy)ethyl acrylate, 1-butoxyethyl acrylate, 1-(2-methylpropoxy)ethyl acrylate, 1-(2 - ethylhexoxy) ethyl acrylate;
pyranyl acrylate, 1-methoxyethyl methacrylate, 1-ethoxyethyl methacrylate, 1-propoxyethyl methacrylate, 1-(1-methylethoxy)ethyl methacrylate, 1-butoxyethyl methacrylate, 1-(2-methyl propoxy)ethyl methacrylate, 1-(2-ethylhexoxy)ethyl methacrylate;
pyranyl methacrylate, di-1-methoxyethyl maleate, di-1-ethoxyethyl maleate, di-1-propoxyethyl maleate, di-1-(1-methylethoxy)ethyl maleate, di-1-butoxyethyl Malate, di-1-(2-methylpropoxy)ethyl maleate, dipyranyl maleate; and the like.

Further, when the polymerization is performed by the surface-initiated living radical polymerization method, the polymerization initiating group to be introduced onto the surface of the base material 10 is not particularly limited as long as it can initiate polymerization. Groups and the like are preferred.

The polymerization initiation group is physically or chemically bonded to the surface of the substrate 10 from the viewpoint of controllability of the graft density and the primary structure (molecular weight, molecular weight distribution, monomer arrangement pattern) of the grafted polymer chain. is preferred.

Methods for introducing (bonding) the polymerization initiation group to the surface of the substrate 10 include a chemical adsorption method, a Langmuir-Blodgett (LB) method, and the like.

For example, when a silicon wafer is used as the substrate 10, 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane is immobilized on the surface of the silicon wafer by chemical bonding of a chlorosulfonyl group (polymerization initiation group). , 2-(4-chlorosulfonylphenyl)ethyltrichlorosilane or the like is used to react with the oxide layer on the surface of the silicon wafer.

Further, when introducing a polymerization initiation group for surface-initiated living radical polymerization to the surface of the base material 10, the polymerization initiation group and a group having bonding property to the base material or a group having affinity for the base material are provided. It is preferable to use a surface treatment agent containing a polymerization initiation group. Such a polymerization initiation group-containing surface treatment agent may be a low-molecular-weight compound or a high-molecular-weight compound.

The surface treatment agent containing a polymerization initiating group is not particularly limited, but a compound having a group capable of bonding to the substrate 10 and a radical generating group is preferable. Initiating group-containing surface treating agents, that is, TEMPO-based, ATRP-based, RAFT-based, and RTCP-based polymerization initiating group-containing surface treating agents can be used. Among these, TEMPO-based, RAFT-based, and RTCP-based polymerization initiation group-containing surface treatment agents are more preferable. Among TEMPO-based surface treating agents containing a polymerization initiating group, DEPN-based surface treating agents containing a polymerization initiating group are particularly preferred. Examples of groups that can be bonded to the substrate 10 include -SiCl ₃ , -Si(CH ₃ )Cl ₂ , -Si(CH ₃ ) ₂ Cl, and -Si(OR) ₃ (in these formulas, R represents methyl, ethyl, propyl or butyl.) and the like. Alternatively, the polymerization initiation group-containing surface treatment agent is described in WO 2006/087839, (2-bromo-2-methyl)propionyloxyhexyltriethoxysilane (BHE), (2-bromo-2 -methyl)propionyloxypropyltriethoxysilane (BPE) and the like can also be used.

Further, from the viewpoint of adjusting the graft density, a silane coupling agent containing no polymerization initiation group (for example, a commonly used alkylsilane coupling agent) may be used in combination with the polymerization initiation group-containing surface treatment agent. good.

The graft density can be freely changed by adjusting the ratio of the polymerization initiation group-containing surface treatment agent and the silane coupling agent containing no polymerization initiation group. In introducing the polymerization initiation group to the surface of the base material 10, the LB method or the vapor phase adsorption method may be adopted from the viewpoints of the uniformity of the polymerization initiation group to be introduced and the controllability of the graft density of the polymerization initiation group. is also possible.

In the LB method, first, a film-forming material is dissolved in a suitable solvent (eg, chloroform, benzene, etc.). Next, after spreading a small amount of this solution on a clean liquid surface, preferably a pure water surface, the solvent is allowed to evaporate or diffuse into the adjacent aqueous phase, resulting in a low density film-forming molecule on the water surface. to form a film of

The diaphragm is then typically mechanically swept over the water surface to compress the membrane by reducing the surface area of the water surface over which the membrane-forming molecules are deployed, thereby increasing the density and forming a dense monolayer on the water surface. get

Next, under appropriate conditions, while maintaining a constant surface density of the molecules that make up the monomolecular film on the water surface, the substrate on which the monomolecular layer is to be deposited is immersed or pulled up in a direction across the monomolecular film on the water surface. transfers the monomolecular film on the water surface onto the substrate 10 and deposits a monolayer on the substrate.

For details and specific examples of the LB method, see Kiyonari Fukuda et al., New Experimental Chemistry Course, Volume 18 (Interface and Colloid), Chapter 6, (1977) Maruzen, Edited by Kiyonari Fukuda, Michio Sugi and Hiroyuki Sasabe, LB Membrane and Electronics, (1986) CMC", "Yoshio Ishii, Practical Techniques for Producing Good LB Films, (1989) Kyoritsu Shuppan".

Then, using the polymerization initiator described above, a polymerization initiating group is introduced onto the surface of the substrate 10, and then the substrate 10 into which the polymerization initiating group has been introduced is immersed in a polymerization reaction solution containing the above-described monomers. By heating according to , it is possible to form polymer chains containing the above-described monomers as polymerized units on the surface of the substrate 10 . In addition to the monomers described above, the polymerization reaction solution can contain various components necessary for the polymerization reaction, such as various radical initiators and solvents.

In the present invention, the polymer chains formed on the surface of the substrate 10 have a graft density of 0.1 to 50% in terms of the exclusive area ratio (occupancy ratio per cross-sectional area of the polymer) with respect to the surface area of the substrate 10. It is preferably formed, more preferably 10-45%, still more preferably 20-40%. The graft density can be calculated from the absolute value of the number average molecular weight (Mn) of the polymer chains, the amount of the grafted polymer, and the surface area of the substrate 10 . Further, the exclusive area ratio in the polymer brush layer 20 can be calculated by obtaining the cross-sectional area from the length of the repeating unit in the stretched form of the polymer and the bulk density of the polymer, and multiplying the cross-sectional area by the graft density. The occupied area ratio means the ratio of the surface of the base material 10 occupied by the graft points (the first monomer) (100% in close packing, no more grafting is possible). By setting the exclusive area ratio of the polymer chains to the surface area of the base material 10 within the above range, the virus inactivation function can be more appropriately enhanced, and the exclusive area ratio is too low or too high. However, the inactivation function against viruses is reduced.

According to the findings of the present inventors, the state of existence of the polymer chains in the polymer brush layer 20 does not necessarily have to be uniform. It may be in an aspect in which portions with dense polymer chains are mixed, and even in such an aspect, the function of inactivating viruses can be sufficiently exhibited. Therefore, when measuring the above-mentioned exclusive area ratio, a relatively wide area range (specifically, an area range of 5 cm × 5 cm) on the surface of the base material 10 is measured, and when the measurement is performed, It is preferable that the area ratio is within the above range.

The graft density per unit area of polymer chains is preferably 0.0005 to 0.4 chains/nm ² , more preferably 0.05 to 0.4 chains/nm ² , and still more preferably 0.1 to 0.4 chains/nm 2 . 0.4 chains/nm ² _, particularly preferably 0.12 to 0.25 chains/nm ² .

The graft density of the polymer chain can be determined, for example, according to the method described in Macromolecules, 31, 5934-5936 (1998), Macromolecules, 33, 5608-5612 (2000), Macromolecules, 38, 2137-2142 (2005), etc. can be measured. Specifically, the graft density (chains/nm ² ) can be obtained by measuring the graft amount (W) and the number average molecular weight (Mn) of the grafted chains and using the following formula.
Graft density (chain/nm ² ) = W (g/nm ² )/M n x (Avogadro's number)
(In the formula, W represents the amount of grafting and Mn represents the number average molecular weight.)

When the base material 10 is a flat substrate, the graft amount (W) is obtained by measuring the thickness of the dry state, that is, the thickness of the grafted polymer chain layer in the dry state by an ellipsometry method, and calculating the thickness of the bulk film. It can be obtained by calculating the graft amount per unit area using the density. Alternatively, when the base material 10 is fibrous or the like, it can be measured by infrared absorption spectrometry (IR), thermogravimetric loss measurement (TG), elemental analysis measurement, or the like.

The number average molecular weight (Mn) of the polymer chains constituting the polymer brush layer 20 is preferably 500 to 10,000,000, more preferably 100,000 to 10,000,000. In addition, the molecular weight distribution (Mw/Mn) of the polymer chains forming the polymer brush layer 20 is preferably close to 1, preferably 1.5 or less, from the viewpoint of further enhancing the virus inactivation function. It is preferably 1.3 or less, more preferably 1.25 or less, even more preferably 1.2 or less, and particularly preferably 1.15 or less. The number average molecular weight (Mn) and the molecular weight distribution (Mw/Mn) of the polymer chains are obtained, for example, by cutting out the polymer chains from the base material 10 by hydrofluoric acid treatment and subjecting the cut polymer chains to gel permeation. A method of measuring with a value converted to polyethylene oxide by a chromatographic method can be mentioned. Alternatively, assuming that the free polymer generated during polymerization has the same molecular weight as the polymer chain introduced into the base material 10, the free polymer is subjected to gel permeation chromatography, and the number average A method of measuring the molecular weight (Mn) and the molecular weight distribution (Mw/Mn) and using them as they are may be employed.

In addition, the average molecular chain length L _p (that is, the polymer brush length) of the polymer chains constituting the polymer brush layer 20 is preferably 10 nm or more, and from a practical point of view, it should be in the range of 10 to 1000 nm. is more preferred. If the average molecular chain length _Lp of the polymer chain is too short, the virus inactivating function may not be sufficient. Also, the average molecular chain length _Lp of the polymer chain can be adjusted by, for example, the type of monomers constituting the polymer chain, polymerization conditions, and the like.

The average molecular chain length _Lp of the polymer chain can be determined from the measurement results obtained by measuring the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the polymer chain. In addition, the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the polymer chains can be obtained by, for example, cutting out the polymer chains from the substrate 10 by hydrofluoric acid treatment, and using the cut-out polymer chains to form a gel. A method of measuring by a permeation chromatography method can be mentioned. Alternatively, assuming that the free polymer generated during polymerization has the same molecular weight as the polymer chains introduced into the substrate 10, the number average molecular weight (Mn) and molecular weight distribution of the free polymer are determined by gel permeation chromatography. A method of measuring (Mw/Mn) and using it as it is may be adopted. The molecular weight distribution (Mw/Mn) of the polymer brush forming the first sliding surface is preferably close to 1, preferably 1.3 or less, more preferably 1.25 or less, and even more preferably It is 1.2 or less, particularly preferably 1.15 or less.

In addition, the ratio (T _b /L _p ) of the thickness T _b of the polymer brush layer 20 to the average molecular chain length L _p constituting the polymer brush layer 20 is preferably 0.001 to 0.6. It is preferably 0.1 to 0.6, more preferably 0.2 to 0.6, particularly preferably 0.3 to 0.5. By setting the ratio (T _b /L _p ) of the thickness T _b of the polymer brush layer 20 to the average molecular chain length L _p within the above range, the virus inactivation function can be further enhanced.

The thickness _Tb of the polymer brush layer 20 is measured by spectroscopic ellipsometry in a state in which the polymer brush layer 20 is vacuum-dried at 25° C. for 1 hour to remove volatile matter mainly containing water. can do. That is, in the present invention, the ratio (T _b /L _p ) of the thickness T _b of the polymer brush layer 20 to the average molecular chain length L _p is the value after removing volatile components. Therefore, when the polymer brush layer 20 contains a volatile component such as water in its use state, the inclusion of water causes the polymer chains constituting the polymer brush layer 20 to approach a fully elongated state. In some cases, the ratio (T _b /L _{p )} exceeds the above range due to the influence of the moisture contained _. A range is preferred. Further, for example, a polymer brush layer swollen with a non-volatile liquid such as a lubricating oil or an ionic liquid maintains the swollen state with the non-volatile liquid such as a lubricating oil or an ionic liquid even after the volatile components are removed. Therefore, even after removing volatile components, the ratio (T _b /L _p ) generally exhibits a large value exceeding 0.6.

In addition, the polymer brush layer 20 preferably has an ionic conductivity of 5.0×10 ⁻¹ S/m or less, more preferably 1.0×10 ⁻¹ S/m or less, still more preferably 5.0×10 −1 S/m or less. Although the lower limit is not particularly limited, it is preferably 1.0×10 ⁻⁴ S/m or ^more . That is, the polymer brush layer 20 does not substantially contain a liquid with a relatively high ionic conductivity (for example, an ionic liquid), so that the ionic conductivity is as low as the above range. A state in which water can be contained, or a state in which water is contained, is preferable from the viewpoint of high adhesion of viruses, and furthermore, from the viewpoint of realizing virus inactivation with high efficiency. The ion conductivity of the polymer brush layer 20 preferably falls within the above range either in a state containing volatile components such as water or in a state not containing volatile components such as water. A method for measuring the ionic conductivity of the polymer brush layer 20 is not particularly limited, but a method of measuring conductivity by a four-probe method (for example, measurement using a resistivity meter (Loresta, manufactured by Nitto Seiko Analytic Co., Ltd.), etc.) can be mentioned. be done.

<Second embodiment>
Next, a second embodiment of the invention will be described.
FIG. 2(A) is a diagram showing a virus inactivating structure according to a second embodiment of the present invention, and FIG. 2(B) is a diagram showing the detailed structure of the IIb portion of FIG. 2(A). 2(C) is a diagram showing the detailed structure of the portion IIc of FIG. 2(A).

As shown in FIG. 2B, the virus inactivating structure according to the second embodiment of the present invention is formed by dispersing a plurality of block copolymer chains 40 in a base polymer 30. there is In addition, the plurality of block copolymer chains 40 includes a polymer block (A) and a polymer block (B) having a lower affinity for the base polymer 30 than the polymer block (A), and It has at least two polymer blocks (A) in the combined chain.

In FIG. 2B, the polymer block (A) constituting the block copolymer chain 40 is indicated by a broken line, and the polymer block (B) is indicated by a solid line. In FIG. 2B, an ABA-type block copolymer chain composed of polymer block (A)/polymer block (B)/polymer block (A) is illustrated as the block copolymer chain 40. , the structure is not limited to such a structure as long as it has at least two polymer blocks (A). For example, it may be an ABAB-type block copolymer chain consisting of polymer block (A)/polymer block (B)/polymer block (A)/polymer block (B), or polymer block (A) /polymer block (B)/polymer block (A)/polymer block (B)/polymer block (A).

Then, as shown in FIG. 2(C), in the virus inactivating structure according to the second embodiment, at least some of the block copolymer chains 40 among the plurality of block copolymer chains 40 are polymer blocks ( A) is present in the base polymer 30 and the polymer block (B) is present in an exposed state from the base polymer 30 . That is, the virus-inactivating structure according to the second embodiment has a structure in which a plurality of loop structures formed in the polymer chain based on the block copolymer chain 40 are exposed on the surface. Specifically, the polymer block (A) exists in the base polymer 30, and a polymer brush structure is formed in which a plurality of polymer chains having a loop structure formed by the polymer block (B) are exposed. It is. Moreover, in the second embodiment, the polymer block (B) has a specific functional group selected from ionic groups, nonionic hydrophilic groups and electron donating groups. Thus, according to the virus inactivating structure according to the second embodiment, similar to the polymer brush layer 20 in the first embodiment described above, it has a high virus inactivating function, and further has a high virus inactivating function. sustainable over the long term.

In the virus inactivating structure according to the second embodiment, a block copolymer chain 40 having a structure of polymer block (A)/polymer block (B)/polymer block (A) is used. Block (A) has a relatively high affinity for the base polymer 30 , while polymer block (B) has a relatively low affinity for the base polymer 30 . Therefore, the polymer block (B) is exposed from the base polymer 30 while the polymer block (A) located on both sides of the polymer block (B) remains in the base polymer 30. A loop structure is formed by the polymer block (B) as shown in 2(C).

In the virus inactivating structure according to the second embodiment, a plurality of block copolymer chains 40 not involved in the loop structure shown in FIG. 2(C) are dispersed in the base polymer 30. (see, for example, FIG. 2(B)). Therefore, for example, when a block copolymer chain 40 involved in the loop structure shown in FIG. Self-healing that such defects can be compensated for by changing the block copolymer chain 40 located in the vicinity of the defective site in the combined chain 40 to one having the loop structure shown in FIG. 2(C). It also has an effect. For example, instead of the method of dispersing the plurality of block copolymer chains 40 in the base polymer 30, the surface of the base polymer 30 is brought into contact with the plurality of block copolymer chains 40, thereby In the case of adopting a configuration in which a loop structure is formed, a self-repairing action for compensating for such defects in the loop structure cannot be expected.

The base polymer 30 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. Thermosetting resins include, for example, epoxy resin, phenol resin, amino resin, unsaturated polyester resin, polyurethane resin, urea resin, melamine resin, heat A curable polyimide resin, a diallyl phthalate resin, and the like are included.

Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polycycloolefin; vinyl resins such as polystyrene, acrylic resin, polyvinyl chloride resin, and polyvinyl alcohol; fluorine resins such as polytetrafluoroethylene. polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and polyethylene naphthalate; silicone resins such as polydimethylsiloxane; and the like.

Examples of rubber include butadiene rubber, styrene butadiene rubber, chloroprene rubber, isoprene rubber, natural rubber, nitrile rubber, diene rubber such as butyl rubber; ethylene propylene rubber, acrylic rubber, polyether rubber, polyurethane rubber, fluororubber, and silicone. Rubber other than diene rubber such as rubber; and the like.

Among these resins or rubbers, polystyrene, acrylic resin, silicone resin, and styrene-butadiene rubber are preferred, acrylic resins being preferred, and among acrylic resins, polybutyl methacrylate is particularly preferred.

The base polymer 30 preferably has a glass transition temperature (Tg) lower than the operating temperature of the composite 10. Specifically, it preferably has a Tg of 50°C or less, and a Tg of 20°C or less. is more preferable.

The block copolymer chain 40 includes a polymer block (A) and a polymer block (B) having a lower affinity for the base polymer 30 than the polymer block (A), and , it is not particularly limited as long as it has at least two polymer blocks (A), but from the viewpoint that the loop structure shown in FIG. 2(C) can be formed in the process, the polymer block (B) It is preferable to use one that is incompatible with the material polymer 30. In particular, the polymer block (B) is incompatible with the base polymer 30, and the polymer block (A) is , which are compatible with the base polymer 30 are particularly preferably used.

Here, that the polymer block (A) is compatible with the base polymer 30 means the following state. That is, after the polymer consisting only of the polymer block (A) and the base polymer 30 are mixed by hot melt mixing or co-solution mixing, the obtained mixture is solidified by cooling or solvent evaporation removal. When measuring the glass transition temperature (Tg) of the sample obtained by When a Tg different from that can be observed, it can be judged to be compatible.

Alternatively, the fact that the polymer block (B) is incompatible with the base polymer 30 refers to the following state. That is, after the polymer consisting only of the polymer block (B) and the base polymer 30 are mixed by hot melt mixing or co-solution mixing, the resulting mixture is solidified by cooling or solvent evaporation removal. When the glass transition temperature (Tg) of the sample obtained by the above was measured, Tg different from these was observed in addition to the Tg of the polymer consisting only of the polymer block (B) and the Tg of the base polymer 30. If not, it can be determined to be incompatible.

As the polymer block (A) and the polymer block (B), those having the above compatibility with the base polymer 30 may be used, but the loop structure shown in FIG. From the ^viewpoint of being able to is preferred, 3 (MPa) ^1/2 or more is more preferred, and 5 (MPa) ^1/2 or more is even more preferred. 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) ^1/2 or less. It is more preferably 0.3 (MPa) ^1/2 or less, further preferably 0.2 (MPa) ^1/2 or less. Furthermore, 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) ^1/2 or more. It is more preferably 3 (MPa) ^1/2 or more, and even more preferably 5 (MPa) ^1/2 or more.

The polymer block (A) is not particularly limited as long as it satisfies the properties described above, and may be selected depending on the relationship with the base polymer 30 to be used. The resin or rubber exemplified as the resin or rubber that constitutes the polymer 30 may be made of a polymer segment that constitutes the resin or rubber.

The molecular weight (weight-average molecular weight (Mw)) of the polymer block (A) portion of the block copolymer chain 40 is not particularly limited, but exhibits sufficient interaction with the base polymer 30, whereby the polymer block (B ) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, more preferably 1,000 to 50,000, and even more preferably is between 1,000 and 20,000. Most preferred is between 2,000 and 20,000.

In addition, the polymer block (B) is not particularly limited as long as it has a specific functional group selected from an ionic group, a nonionic hydrophilic group and an electron donating group and satisfies the properties described above. However, it is preferably a polymer block formed by polymerizing a monomer mixture containing a monomer having a specific functional group. As in the embodiment, a monomer having an ammonium group as a specific functional group (more preferably, a monomer capable of introducing an ammonium group into the side chain of the polymer chain, particularly preferably represented by the above general formula (1) It is more preferable that it is a polymer block formed by polymerizing a monomer mixture containing a compound having a specific functional group. They may be used together. Moreover, as a monomer for forming a polymer chain, a monomer copolymerizable with a monomer having a specific functional group (monomer having no specific functional group) may be used.

Further, as in the first embodiment described above, instead of the compound represented by the general formula (1), or together with the compound represented by the general formula (1), for example, a (meth)acrylic acid-based monomers, styrenic monomers, monofunctional monomers having one addition-polymerizable double bond, hydrophobic monomers, hydrophilic monomers, monomers having carboxyl groups in side chains or groups that can be easily converted to carboxyl groups, etc. may be used.

The molecular weight (weight-average molecular weight (Mw)) of the polymer block (B) portion of the block copolymer chain 40 is not particularly limited, but the molecular weight of the polymer block (B) portion is the length of the formed loop (loop structure It is closely related to the length of the loop that constitutes it). The larger the molecular weight of the polymer block (B) portion, the larger the loop length formed on the surface of the composite 10 . That is, the polymer loop layer (layer having a loop structure formed by the polymer block (B) portion) is thickened. On the other hand, if the molecular weight of the polymer block (B) portion is small, the polymer loop layer will be thin. Considering the phenomenon of breaking the loop brush due to irregularities on the sliding surface facing the loop brush layer, the molecular weight (weight average molecular weight (Mw)) of the polymer block (B) portion is preferably 1,000 to 200,000, or more. It is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 20,000.

The method for synthesizing the block copolymer chain 40 is not particularly limited, but the block copolymer chain 40 is an ABA-type block copolymer consisting of polymer block (A)/polymer block (B)/polymer block (A). When it is a coalesced chain, it can be synthesized by the following method. That is, a method of forming polymer blocks (A) on both sides of the polymer block (B) by polymerizing a monomer forming the polymer block (A) in the presence of the polymer block (B); Examples thereof include a method of polymerizing the monomers forming the polymer block (B) in the presence of the block (A), and then further polymerizing the monomers forming the polymer block (A). A living radical polymerization method can be very suitably used as a method for obtaining a block copolymer having a narrow molecular weight distribution and capable of controlling the molecular weight of each block. Among them, the atom transfer radical polymerization method can be particularly preferably used.

In addition, the polymer block (A) and the polymer block (B) may be directly bonded, or the monomer forming the polymer block (A) and the monomer forming the polymer block (B) may be It may be linked via a monomer other than the mer or an oligomer block consisting of such a monomer. Further, the plurality of polymer blocks (A) contained in the block copolymer chain 40 may be substantially the same polymer blocks (that is, blocks composed of substantially the same monomer units). However, they may be different polymer blocks. Furthermore, even when a plurality of polymer blocks (B) are included in the block copolymer chain 40, the plurality of polymer blocks (B) are substantially the same polymer block (i.e., substantially the same monomer units), or polymer blocks different from each other.

Further, in the second embodiment, the ion conductivity of the polymer brush layer formed by the plurality of block copolymer chains 40 is preferably 5.0×10 ⁻¹ S/m or less, more preferably 1.0×10 −1 S/m or less. It is 0×10 ⁻¹ S/m or less, more preferably 5.0×10 ⁻² S/m or less, and although the lower limit is not particularly limited, it is preferably 1.0×10 ⁻⁴ S/m or more. The ionic conductivity of the polymer brush layer can be measured by the same method as in the first embodiment described above.

According to the second embodiment, a polymer brush structure is provided in which a plurality of polymer chains having a loop structure formed by the polymer block (B) are exposed, and the polymer block (B) includes an ionic group and a nonionic group. It has a specific functional group selected from a hydrophilic group and an electron-donating group. Therefore, as in the above-described first embodiment, by having a specific functional group contained in the polymer brush structure composed of the polymer block (B) exposed in a loop shape, it is easy to fuse with the envelope that constitutes the virus, and further. Since it is composed of a plurality of polymer chains, it exhibits high osmotic pressure, and it can be said that it exhibits a high virus-inactivating function. In addition, since the polymer brush structure composed of the polymer block (B) is composed of a polymer brush structure composed of a plurality of polymer blocks (B), such a high virus inactivation function can be achieved by changing its structure. Therefore, it can be said that the high virus inactivation function can be sustained for a long period of time.

In the second embodiment, as the block copolymer chain 40, an ABA-type block copolymer chain composed of polymer block (A)/polymer block (B)/polymer block (A) is used. A structure having a polymer brush structure in which a plurality of polymer chains having a loop structure formed by the polymer block (B) are exposed is exemplified. The structure may be such that a coalescing chain is used whereby the polymer block (B) is exposed without forming a loop structure.

<Third Embodiment>
Next, a third embodiment of the invention will be described.
FIG. 3 shows a virus inactivation structure according to a third embodiment of the invention. As shown in FIG. 3, the virus inactivating structure according to the third embodiment is a branched polymer 50. As shown in FIG. As shown in FIG. 3, the branched polymer 50 has a plurality of polymer graft chains (side chains) 52 from a linear main chain (a linear polymer chain serving as the main chain) 51 as a substrate. It has a branched structure. The branched polymer 50 has a shape like a bottle brush (a cleaning brush for cleaning a container having a bottle structure).

The branched polymer 50 has a branched polymer structure in which a plurality of side chains 52 are branched from a linear main chain 51 as described above. It is composed of a plurality of repeating units containing carbon atoms and hydrogen atoms linked together. In addition, in the branched polymer 50, the side chain 52 has a specific functional group selected from an ionic group, a nonionic hydrophilic group and an electron donating group, and the branched polymer 50 has such a side chain 52, it has a virus inactivation function.

The number average degree of polymerization of the main chain 51 is preferably 10-10,000, more preferably 10-1,000, still more preferably 10-100. The number average degree of polymerization of the main chain 51 is not particularly limited, but the number average molecular weight of the main chain precursor before introducing the side chain 52 is measured, and the measured number average molecular weight is divided by the monomer unit molecular weight. can be found at

The side chain 52 may be linear, or may have a branched structure or a crosslinked structure. The number average degree of polymerization of the side chains 52 is preferably 1-1,00, more preferably 1-50, and even more preferably 5-20. The method for measuring the number average degree of polymerization of the side chain is not particularly limited. A trace amount of an agent (for example, an organic compound having a halogen-substituted carbon group) is added to simultaneously synthesize a free polymer having a repeating structure common to the polymer chain of the side chain 52, and the free polymer is measured. The obtained number average degree of polymerization can be used as the number average degree of polymerization of the side chain 52 .

The number average molecular weight (Mn) of the entire branched polymer 50 including the main chain 51 and side chains 52 is preferably 1,000 to 10,000,000, more preferably 1,000 to 1,000,000. , more preferably 5,000 to 500,000. The number-average molecular weight of the branched polymer 50 as a whole can be measured by gel permeation chromatography as a polystyrene-equivalent value.

The density of side chains branched from the main chain is the number per 1 nm of main chain path length (chain/nm), preferably 1 chain/nm or more, more preferably 2 chains/nm or more, and still more preferably 3 chains. /nm or more. Here, the density of side chains can be determined from the graft efficiency.

As shown in FIG. 3, the branched polymer 50 used in the third embodiment has a structure in which a plurality of side chains 52 are branched from a linear main chain 51 as a substrate, and a plurality of side chains 52 are branched. The chain 52 is not particularly limited as long as it has a specific functional group selected from an ionic group, a nonionic hydrophilic group and an electron donating group. The branched polymer 50 can be produced, for example, by graft polymerizing a monomer mixture containing a monomer having a specific functional group to a polymer for forming the main chain 51 by a known graft polymerization method. . As the branched polymer 50, as in the above-described first embodiment, a monomer having an ammonium group as a specific functional group (more preferably, a monomer capable of introducing an ammonium group into the side chain of the polymer chain) , and particularly preferably the compound represented by the above general formula (1)) is preferably produced by graft polymerization of a monomer mixture. In addition, as a monomer having a specific functional group, one type may be used alone, or two or more types may be used in combination. Moreover, as a monomer for forming a polymer chain, a monomer copolymerizable with a monomer having a specific functional group (monomer having no specific functional group) may be used.

Further, as in the first embodiment described above, instead of the compound represented by the general formula (1), or together with the compound represented by the general formula (1), for example, a (meth)acrylic acid-based monomers, styrenic monomers, monofunctional monomers having one addition-polymerizable double bond, hydrophobic monomers, hydrophilic monomers, monomers having carboxyl groups in side chains or groups that can be easily converted to carboxyl groups, etc. may be used.

Further, in the third embodiment, as the branched polymer 50, a plurality of branched polymers 50 forming a crosslinked structure may be used, or the plurality of branched polymers 50 may be composed of ionic bonds, Those bonded to each other by hydrogen bonding, hydrophobic interaction, or the like may be used. Alternatively, a base material or filler is used, a polymerization initiating group is introduced to the surface of the base material or filler, and a polymerization reaction is performed on the base material or in a state containing the filler to obtain a branched polymer. 50 may be on a substrate or composited with a filler. When a plurality of branched macromolecules 50 are compounded on a base material, a polymer brush layer composed of a plurality of branched macromolecules 50 can be formed on the base material. In this case, the ionic conductivity of the polymer brush layer composed of the plurality of branched polymers 50 is preferably 5.0×10 ⁻¹ S/m or less, more preferably 1.0×10 ⁻¹ S/m. m or less, more preferably 5.0×10 ⁻² S/m or less, and although the lower limit is not particularly limited, it is preferably 1.0×10 ⁻⁴ S/m or more. The ionic conductivity of the polymer brush layer can be measured by the same method as in the first embodiment described above.

A branched polymer 50, which is a virus-inactivating structure according to the third embodiment, has a structure in which a plurality of polymer graft chains (side chains) 52 are branched from a main chain 51. The side chains 52 are composed of ions It has a specific functional group selected from a functional group, a nonionic hydrophilic group and an electron donating group. Therefore, as in the first embodiment described above, due to the action of the specific functional group contained in the side chain 52, it is easy to fuse with the envelope that constitutes the virus, and furthermore, it is composed of a plurality of polymer chains. Therefore, it can be said that it exhibits a high osmotic pressure and thereby exerts a high virus-inactivating function. In addition, since the branched polymer 50 has a bottle-brush-like structure with a plurality of side chains 52, it stably exhibits such a high virus-inactivating function without undergoing structural changes or the like. Therefore, it can be said that the high virus inactivation function is sustainable over a long period of time.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

<Example 1>
(Formation of polymer brush layer)
Surface initiated atom transfer radical polymerization (ATRP) of N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide (DEMM-TFSI) was performed as follows. gone.
That is, first, 26.0 mg (0.13 mmol) of 2,2′-bipyridine (Bipy), N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoro 1.96 g of methylsulfonyl)imide (DEMM-TFSI) and 8.0 g of acetonitrile were added, and argon was bubbled for 10 minutes to degas the solution. The flask was then transferred to an argon-purged glovebox, 5.2 mg (0.052 mmol) of Cu(I)Cl and 0.78 mg (0.0058 mmol) of Cu(II) _Cl2 were added, and the flask was capped with a three-way stopcock. installed. After that, the flask was taken out from the glove box while the cap was closed to keep the sealed state, and the flask was stirred in an oil bath at 60° C. to completely dissolve the copper and Bipy. The flask was then transferred to a glove box, and the solution was filtered through a membrane filter (pore size: 0.2 µm). A vacuum pump was then used to volatilize and remove the acetonitrile. The purpose of adding acetonitrile in the above procedure is to lower the viscosity of the solution and promote the dissolution of copper and Bipy as a ligand. In addition, in order to suppress precipitation of copper chloride during the polymerization process, the reaction was carried out using a ligand (Bipy) in a molar amount of 10% excess relative to the required molar amount relative to copper. Next, 8.0 g (16.6 mmol) of DEMM-TFSI and 0.65 mg (0.0033 mmol) of ethyl 2-bromoisobutyrate (2-(EiB)Br) were placed in another Schlenk tube, and argon was bubbled for 20 minutes. to degas the mixture. A non-volatile ATRP polymerization solution was prepared by putting the obtained solution into a Schlenk tube and a flask and mixing them. The molar composition ratio in the resulting ATRP polymerization solution was [DEMM-TFSI] ₀ /[2-(EiB)Br] ₀ /[Cu(I)Cl] ₀ /[Cu(II)Cl ₂ ] ₀ /[ Bipy] ₀ =5000/1/20/5/50.

Next, after filtering the ATRP polymerization solution thus obtained, the filtered ATRP polymerization solution is centrifuged at 500 x g for 10 minutes using a centrifuge installed in the glove box. Thus, the defoaming operation was performed. Filtration and defoaming operations are not recommended because if undissolved solid components of copper chloride or air bubbles mixed in during solution preparation adhere to substrates such as silicon wafers and glass, polymer brushes cannot be formed in those areas. This is an operation to prevent

Then, in a glove box, a filtration operation and a An ATRP polymerization solution subjected to a defoaming operation was applied. Then, an ATRP polymerization reaction was carried out in an incubator (installed in a glove box) set at a temperature of 70°C. The ATRP polymerization solution prepared above is prepared only with non-volatile components and has a relatively high viscosity, so it is maintained as a liquid layer with a thin liquid film on the silicon wafer until the polymerization is completed. It had been. In this ATRP polymerization reaction system, the polymerization conversion rate of the monomer reached 99% after 70 hours, and the polymer brush layer had a plurality of polymer chains with a number average molecular weight of 1,826,000 and a molecular weight distribution (Mw/Mn) of 1.20. was formed on a silicon wafer. The resulting polymer brush layer had a dry film thickness T _b (film thickness after vacuum drying at 25°C for 1 hour) measured by spectroscopic ellipsometry of 515 nm, and a graft density of 0 measured by the above method. 0.15 strands/nm ² and a surface coverage of 35% was calculated. Further, the ratio (T _b /L _p ) of the thickness T _b of the polymer brush layer to the average molecular chain length L _p of the plurality of polymer chains constituting the polymer brush layer, calculated by the above method, was 0.41. The ionic conductivity of the polymer brush layer measured by conductivity measurement by the 4-terminal method (using a resistivity meter (Loresta, manufactured by Nitto Seiko Analytic Co., Ltd.)) was 1.60 × 10 ^-2 S / m. there were. Separately, a polymer of DEMM-TFSI was prepared and dispersed in water at pH = 7 at 1% by weight, and when the absorbance was measured, the absorbance was 0.3 or less, indicating water solubility. Met.

(Evaluation of virus inactivation)
After sterilizing the silicon wafer (1 cm×1 cm) on which the polymer brush layer was formed, 3 μL of the virus solution (bovine herpes virus solution) was dropped on the surface on which the polymer brush layer was formed. After spreading the virus solution on the surface on which the polymer brush layer was formed, it was covered with a cover glass and allowed to stand at room temperature for 5 minutes. After 5 minutes, the silicon wafer on which the polymer brush layer was formed was placed in a test tube together with 500 μL of the culture medium (MEM), and stirred with a vortex mixer for 10 seconds to form a layer on the surface of the polymer brush layer. Adhering virus was released into the culture medium. Next, a portion of the culture medium was extracted, and the extracted culture medium was inoculated into cells and counted as the number of detected plaques to evaluate the virus inactivation effect.
In the evaluation of the virus inactivating effect, the same measurement as above was performed on a glass plate on which no polymer brush layer was formed, and the number of plaques counted was compared. As a result, the number of detected plaques (average: 11) on the silicon wafer with the polymer brush layer was 7% compared to the number of plaques (average: 157) detected on the glass plate without the polymer brush layer. became. That is, the result was a 93% reduction in the number of viruses.

Further, the same measurement as above was performed by changing the stationary time from 5 minutes to 30 minutes. As a result, the number of detected plaques (average: 1.3) on the silicon wafer on which the polymer brush layer was formed was higher than the number of plaques detected on the glass plate (average: 104.3) on which the polymer brush layer was not formed. , 1.2%. That is, the result was a 98.8% reduction in the number of viruses.

Furthermore, the silicon wafer on which the polymer brush layer was formed (standing time: 30 minutes) on which the virus inactivation was evaluated was washed with distilled water, and the virus inactivation was evaluated again (standing time: 30 minutes). As a result (i.e., evaluation by reuse), the number of plaques detected on a silicon wafer with a polymer brush layer was lower than the number of plaques detected on a glass plate without a polymer brush layer. less than 10%. That is, the result was that the number of viruses was reduced by 90% or more.
In addition, instead of washing with distilled water, washing with a 70% ethanol aqueous solution was performed, and evaluation was performed in the same manner as described above. It was less than 10% of the number of plaques detected on the uncoated glass plate. That is, the result was that the number of viruses was reduced by 90% or more.

From the above, according to the polymer brush containing a plurality of polymer chains having specific functional groups selected from ionic groups, nonionic hydrophilic groups and electron donating groups, it is possible to achieve high virus inactivation function. It can be confirmed that such a high virus inactivation function is sustainable over a long period of time.

<Example 2>
(Formation of polymer brush layer)
using (2-bromo-2-methyl)propionyloxyhexyltriethoxysilane (BHE) instead of (2-bromo-2-methyl)propionyloxypropyltriethoxysilane (BPE) as an immobilized initiator and A polymer brush layer was formed on silica particles in the same manner as in Example 1, except that silica particles were used instead of silicon wafers. The obtained polymer brush layer was quantified by thermogravimetric analysis, and the weight fraction of the polymer content was 8.9%. The graft density was calculated to be 0.15 chains/nm ² and the surface coverage was calculated to be 34%, as measured by the method described above. In Example 2, considering the production conditions and the like, the number average molecular weight and molecular weight distribution (Mw/Mn) of the polymer chains constituting the polymer brush layer, the dry film thickness T _b of the polymer brush layer, the polymer brush layer It can be said that the ratio (T _b /L _p ) of the thickness T _b of the polymer brush layer and the ionic conductivity of the polymer brush layer are almost the same as in Example 1.

(Evaluation of virus inactivation)
1.0 g of the resulting silica particles forming a polymer brush layer were dispersed in 200 mL of a solvent in which equal volumes of a 0.5 M acetonitrile acetate solution and water were mixed to obtain an acetic acid dispersion of silica particles forming a polymer brush layer. got Then, 0.925 mL of the acetic acid dispersion of the obtained silica particles forming the polymer brush layer, 100 μL of virus solution (bovine herpes virus solution), and 1.475 mL of phosphate buffered saline (PBS) are placed in a test tube. Thus, a test solution was prepared. Then, after collecting 25 μL of the obtained test solution (sample after preparation), perform a shaking operation for 1 hour, collect 25 μL of the test solution after shaking for 1 hour (sample shaken for 1 hour), After shaking for 1 hour, 25 μL of the test solution (sample shaken for 2 hours) was sampled. Then, the sample after preparation, the sample shaken for 1 hour, and the sample shaken for 2 hours were diluted 10,000-fold with culture medium (MEM), inoculated into cells, allowed to stand for 1 hour, and then methylcellulose medium was added. After overlaying and culturing for 2 days, virus inactivation effect was evaluated in the same manner as in Example 1. In Example 2, a sample using silica particles that did not form a polymer brush layer was also produced under the same conditions and used for comparison. As a result, even in Example 2, a virus inactivation function equivalent to that in Example 1 was confirmed.

Claims (9)

A virus-inactivating structure having a virus-inactivating function, comprising a polymer brush structure comprising a plurality of polymer chains having functional groups selected from ionic groups, non-ionic hydrophilic groups and electron-donating groups. 2. The virus-inactivating structure according to claim 1, wherein said polymer chains are water-soluble. 3. The virus-inactivating structure according to claim 1 or 2, wherein a plurality of said polymer chains are covalently fixed on a substrate to form a polymer brush structure. The ratio (T _b /L _p ) of the thickness T _b of the polymer brush structure to the average molecular chain length L _p of the polymer chains constituting the polymer brush structure is 0.001 to 0.6. Item 4. The virus inactivating structure according to item 3. 5. The virus inactivating structure according to claim 3 or 4, wherein the base material is fiber, monofilament, twisted yarn, woven fabric, nonwoven fabric, cut fiber, hollow fiber, glass, metal, or processed products thereof. wherein at least one end of the plurality of polymer chains is present in the base polymer and at least a portion thereof is exposed from the base polymer to form a polymer brush structure. 3. The virus inactivating structure according to 1 or 2. 3. The antivirus according to claim 1 or 2, wherein the plurality of polymer chains are polymer graft chains branched from a polymer chain serving as a main chain, thereby forming a bottle brush-like polymer brush structure. activation structure. The virus inactivating structure according to any one of claims 1 to 7, wherein the polymer brush structure has an ionic conductivity of 5.0 × 10 ^-1 S/m or less. 9. The virus-inactivating structure according to any one of claims 1 to 8, wherein said polymer chains have an ammonium group.

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