WO2008020618A1

WO2008020618A1 - Polyrotaxane-containing material exerting high diffusion coefficient

Info

Publication number: WO2008020618A1
Application number: PCT/JP2007/066000
Authority: WO
Inventors: Kohzo Ito; Yanli Guo; Changming Zhao
Original assignee: The University Of Tokyo; Advanced Softmaterials Inc.
Priority date: 2006-08-18
Filing date: 2007-08-17
Publication date: 2008-02-21
Also published as: JP2008045055A

Abstract

A material (such as wet gel) having a high diffusion coefficient, namely, a material which comprises the first polyrotaxane (i), a substance (ii) consisting of the first polymer (a) other than polyrotaxanes and/or the second polyrotaxane (b), a solvent (iii), and the first solute (iv) with at least part of the first polyrotaxane (i) and at least part of the substance (ii) being chemically and/or physically crosslinked with each other and which satisfies the requirement that the effective diffusion coefficient, D/q1/3 (wherein D is diffusion coefficient and q is degree of swelling of material), of the first solute in the material must be at least 1.1 times the effective diffusion coefficient of the second solute in a reference sample which consists of poly(acrylamide), water, tris hydrochloride buffer, and disodium 3-hydroxy-4-[(2,4,5-tri-methylphenyl)azo]-2,7– naphthalenedisulfonate as the second solute and has a water content of 95%.

Description

Specification

Materials with poly-oral taxanes that provide high diffusion coefficients

Technical field

[0001] The present invention relates to a material having a polyoral taxane that provides a high diffusion coefficient.

Background art

[0002] Cyclic molecules (rotators) are cyclically attached to both ends (both ends of a linear molecule) of a pseudopolyrotaxane in which the opening of a circular molecule (axis: axis) is included in a skewered manner. A cross-linked polyrotaxane formed by cross-linking a plurality of polymouth taxanes in which blocking groups are arranged so that molecules are not detached has been proposed (see Patent Document 1, which is incorporated herein by reference in its entirety) Incorporated into the book).

[0003] This crosslinked polymouth taxane has a pulley effect in which a cyclic molecule moves on a linear molecule, so that even if tension is applied to the crosslinked polymouth taxane, the tension is exerted by the pulley effect. Can be uniformly dispersed in the crosslinked poly (oral) taxane. The crosslinked polytaxane also has a function of retaining a solvent such as water. Due to these functions, the crosslinked poly (taxane) taxane is expected to be applied in various fields.

[0004] On the other hand, various types of wet gels have been proposed as materials for holding a solvent such as water (see Non-Patent Document 1).

Patent Document 1: Japanese Patent No. 3475252.

Non-patent literature l: Tokita, M., Jpn. J. Appl. Phys. 34, 2418-2422 (1995).

Disclosure of the invention

Problems to be solved by the invention

[0005] However, conventionally proposed! /, Such as wet gel, did not have a sufficiently high diffusion coefficient. For example, contact lenses and DDS (drug delivery system)

The force for which a material having a higher diffusion coefficient, such as a wet gel, has been sought, has not yet been met.

[0006] Therefore, an object of the present invention is to provide a material having a high! / Diffusion coefficient, such as a wet gel. Another object of the present invention is to provide a material having a high diffusion coefficient and high permeability, such as a wet genore.

Means for solving the problem

The present inventors have found the following invention that should achieve the above object.

<1> i) the first poly oral taxane,

ii) the following substances a) and / or b):

a) a first polymer that is other than a polymouth taxane;

b) a second polymouth taxane,

iii) solvent, and

iv) the first solute;

A material having

The i) at least a part of the first polyoral taxane and the ii) at least a part of the substance are chemically and / or physically crosslinked,

The first polymouth taxane includes a first cyclic molecule, a first linear molecule that skewers the first cyclic molecule, and the first cyclic molecule from the first linear molecule. A first blocking group disposed at both ends of the first linear molecule so that the molecule does not desorb, and the second polymouth taxane is the same as the first cyclic molecule, The second cyclic molecule may be a second linear molecule that includes the second cyclic molecule in a skewered manner, and may be the same as or different from the first linear molecule. Second linear molecule, and a second blockade disposed at both ends of the second linear molecule so that the second cyclic molecule is not detached from the second linear molecule. The same as or different from the first blocking group! /, Having a second blocking group,

The effective diffusion coefficient D / q ^{1/3 of} the first solute in the material (D: diffusion coefficient, q: swelling degree of the material) is poly (acrylamide), water, Tris-HCl buffer, and second This is a comparative sample consisting only of disodium 3-hydroxy _4- [(2,4,5-trimethylphenenole) azo] -2,7-naphthalenedisulfonate as a solute of water with a water content of 95%. 1.1 times or more, preferably 1.2 times or more, for example 1.;! To 10 times, preferably 1.2 to 10 times, of the effective diffusion coefficient of the second solute in the comparative sample More preferably 2 to 10 times, still more preferably 3 to 1 The above material, which is 0 times, most preferably 5 to 10 times.

In addition, disodium 3-hydroxy _4- [(2,4,5-trimethylphenyl) azo] -2,7-naphthalenedisulfonate is generally known as S “Ponceau 3R” It is a red pigment.

<0008> <2> In the above item 1), ii) material strength a) having a first polymer, wherein at least a part of the first polymouth taxon and at least a part of the first polymer are chemically And / or physically cross-linked.

<3> In the above item <1> or <2>, at least a part of the first polymouth taxane and

It is preferable that at least a part of one polymer is chemically bonded via a cyclic molecule.

[0009] <4> In any of the above <1> to <3>, the substance M, 1 ₃ ) having a second polyrotaxane, and at least a part of the first polytaxane It is preferable that at least a part of the second poly-ortaxane is chemically and / or physically crosslinked.

<5> The above 1> to 4>! /, Or even! /, And at least a portion of the first polyoral taxane and at least a portion of the second polyortaxane are cyclic molecules. It is better to chemically bond via the.

<6> In the above <1> to <5> !, or in any case, the solvent is selected from the group consisting of water, a non-aqueous solvent, and a mixture of water and a non-aqueous solvent. Good.

[0010] <7> In <6> above, non-aqueous solvent power S, natural oil (eg, glycerin, castor oil, olive oil, etc.); alcohols (eg, methanol, ethanol, n-propanol, isopropanol, n- Monohydric alcohols such as butanol and 2-butanol; and ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol , Hexylene glycolol, otylene glycolol, polyethylene glycolol, polypropylene glycol, polyhydric alcohols such as polyester polyols; fatty acids (especially higher fatty acids such as oleic acid, linolenic acid, etc.); ethers (such as polyhydric alcohols) No Kill ethers, Echirenokishido 'propylene O sulfoxide copolymer); selected from the group consisting of and silicone oils (e.g., dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil); Abie Chin acid Echiru It is good. The alkyl ethers of polyhydric alcohols may be monoalkyl ethers or polyalkyl ethers! /. Examples include polymethyl alcohol monomethyl ether, dimethyl ether, monoethyl ether, and jetyl ether. For polyethylene glycol, the number average molecular weight is 200 to 600, preferably 200 to 450. For polypropylene glycol, the number average molecular weight force is preferably 400 to 5000, more preferably 400 to 3500.

[0011] <8> In any one of the above items <1> to <7>, the weight ratio of the solvent to the poly (taxane taxane)

(Solvent: Polymouth Taxane) Force 1: 99-99.9: 0.1, preferably (or 5: 95-99.9: 0.1, more preferably 10: 90-99.9: 0.1 There should be.

<9> In any one of the above items <1> to <8>, the first solute is a gas molecule, an acid, a base, a chloride, an iodide, a lithium salt, a metal ion, a polyhydric alcohol, polyethylene dallicol and its Derivatives, lipids, fatty acids, saccharides, amino acids and derivatives thereof, vitamins and derivatives thereof, dye molecules, drug molecules (for example, an anti-cancer agent such as anthalacycline anti-cancer symmetric U-actinomycin, dactinomycin, bleomycin, daunomycin, Cisplatin and its derivatives such as, but not limited to, adriamycin, idamycin, mitomycin, etc. Anti-inflammatory agents include, but are not limited to, dexamethasone, indomethacin, menthol, etc.), Colloidal particles, biomolecules (eg proteins Quality, DNA, RNA, etc.).

[0012] <10> In any one of the above items <1> to <9>, the material strength is an external medicine (for example, a base material for external application such as an analgesic / anti-inflammatory agent, a base material for skin application); Carrier material (for example, anticancer drug carrier targeting cancer cells); Wound dressing; Water purifier (for example, remover of harmful metals and spoiled odor in marsh, factory effluent, hot spring water and mine wastewater) Cosmetics (eg gel face mask material, gel cream); cell culture medium (eg cell propagation medium, cell differentiation medium etc.); plant tissue culture medium (eg hydroponic culture); battery electrolyte (eg lithium Selected from the group consisting of ion conductive electrolyte materials and electrolytes for fuel cells); and contact lenses!

[0013] <11> In any one of the above items <1> to <10>, the first and / or second straight chain The molecule is poly (bull alcohol), poly (b) pyrrolidone, poly (meth) acrylic acid, cellulose-based lunar effect (canolepoxymethylenoresenorelose, hydroxyethinoresenorelose, hydroxypropylcellulose, etc.), polyacrylamide, Polyethylene oxide, polyethylene glycol, polypropylene glycol, polybulacetal resin, polybulumethyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, etc. and / or copolymers thereof, polyethylene, polypropylene, and Other polyolefin resins such as copolymer resins with olefin monomers, polyester resins, polychlorinated butyl resins, polystyrene resins such as polystyrene and acrylonitrile monostyrene copolymer resins, Acrylic resins such as talylate, (meth) acrylic acid ester copolymer, acrylonitrile methyl acrylate copolymer resin, polycarbonate resin, polyurethane resin, chlorinated butyl acetate copolymer resin, polybutyl pentyl resin, etc .; and these Derivatives or modified products, polyisobutylene, polytetrahydrofuran, polyaniline, attarilonitrile tributadiene styrene copolymer (ABS resin), polyamides such as nylon, polyimides, polyisoprene, polybutadienes such as polybutadiene, polydimethylol Polysiloxanes such as siloxane, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and these Preferably selected from the group consisting of derivatives, for example, selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene. Is preferably selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene, particularly polyethylene glycol.

<12> According to any of the above <1> to <11>, the first and / or second linear molecule has a molecular weight of 10,000 or more, preferably 20,000 or more, more preferably It should be 30,000 or more.

<13> According to any of the above <1> to <12>, the first and / or second blocking force S, dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, Fluoresceins, pyrenes, substituted benzenes (as substituents, alkyl, alkyloxy Examples include, but are not limited to, cis, hydroxy, halogen, cyano, sulfonyl, canolepoxinole, amino, phenol and the like. One or more substituents may be present.

), Optionally substituted polynuclear aromatics (but not limited to the same as the substituents mentioned above, one or more substituents may be present), and Preferably selected from the group consisting of Lloyds. The adamantane group or the trityl group is more preferably selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, and pyrenes. .

<14> In any one of the above items <1> to <13>, the first and / or second cyclic molecules are substituted! Yo!

<15> According to any one of the above items <1> to <14>, the first and / or second cyclic molecule may be substituted, and the cyclodextrin molecule is a -Selected from the group consisting of cyclodextrin, 13-cyclodextrin and γ-cyclodextrin, and derivatives thereof.

[0016] <16> In any one of the above items <1> to <15>, the first and / or second cyclic molecule may be substituted α-cyclodextrin, and the first and / or first The two linear molecules should be polyethylene glycol.

<17> In any of <1> to <16> above, when the first cyclic molecule is skewered by the first linear molecule, the first cyclic molecule is included to the maximum extent. The first cyclic molecular force is 0.001 -0.6, preferably 0.01 -0.5, more preferably 0.05-0.4, where It is preferable that the chain molecules are included in a skewered manner. In addition, when the amount of inclusion of the second cyclic molecule to the maximum when the second cyclic molecule is clasped by the second linear molecule is 1, the second cyclic molecule is Should be included in a skewered manner in the second linear molecule in an amount of 0.001 -0.6, preferably 0.01 -0.5, more preferably 0.05 -0.4. .

[0017] <18> i) a first poly oral taxane,

ii) the following substances a) and / or b):

a) a first polymer that is other than a polymouth taxane; b) a second polymouth taxane,

iii) solvent, and

iv) a method for producing a material having a first solute;

A) The first cyclic molecule, the first linear molecule that includes the first cyclic molecule in a skewered manner, and the first cyclic molecule so that the first cyclic molecule is not detached from the first linear molecule. Providing a first poly-ortaxane having a first blocking group disposed at both ends of one linear molecule;

B) The following steps a ′) and / or): ii) preparing the substance,

a ') providing a first polymer; or

b ') a step of preparing a second poly-oral taxane, which may be the same as or different from the first cyclic molecule! /, the second cyclic molecule, and the second cyclic molecule being skewered A second linear molecule that is included in the form of a second linear molecule, which may be the same as or different from the first linear molecule, and the second linear molecule The second cyclic molecule is not detached! / It is a second blocking group disposed at both ends of the second linear molecule, and is different even if it is the same as the first blocking group. Providing a second polymouth taxane having an optional second blocking group;

C) a step of chemically and / or physically cross-linking i) at least a part of the first polyoral taxane and ii) at least a part of the substance to obtain a cross-linked polyoral taxane;

D) preparing a solution having said iii) solvent and iv) a first solute; and

E) contacting the cross-linked polymouth taxane with the solution to obtain the material;

The effective diffusion coefficient D / q ^{1/3 of} the first solute in the material (D: diffusion coefficient, q: swelling degree of the material) is poly (acrylamide), water, Tris-HCl buffer, and second This is a comparative sample consisting only of disodium 3-hydroxy _4-[(2,4,5-trimethylphenol) azo] -2,7-naphthalenedisulfonate as a solute of water with a water content of 95%. 1.1 times or more, preferably 1.2 times or more, for example 1.;! To 10 times, preferably 1.2 to 10 times, of the effective diffusion coefficient of the second solute in the comparative sample More preferably 2 to; 10 times, still more preferably 3 to 10 times, most preferably 5 to 10 times.

<19> In the above item 18>, ii) the substance has a) the first polymer, and in step C) In this case, it is preferable to chemically and / or physically cross-link at least a part of the first polyoral taxane and at least a part of the first polymer.

<20> In step C) of <18> or <19> above, at least a portion of the first polyoral taxane and at least a portion of the first polymer are chemically bonded via a cyclic molecule. It is better to let it go.

[0019] <21> In any one of the above items <18> to <20>, ii) the substance has b) a second polyrotaxane, and in step C), in step C, It is preferred to chemically and / or physically cross-link at least a portion of the second polymouth taxane.

<22> In the process C) of any one of the above 18> to 21>, at least a part of the first polyoral taxane and at least a part of the second polyoral taxane are bonded via a cyclic molecule. It should be chemically bonded.

[0020] <23> i) a first poly-oral taxane,

ii) the following substances a) and / or b):

a) a first polymer that is other than a polymouth taxane;

b) a second polymouth taxane,

iii) solvent, and

iv) a method for producing a material having a first solute;

B) by the following steps a ′) and / or b ′): ii) preparing the substance, a ′) preparing the first polymer or precursor thereof; or

b ') a step of preparing a second poly-oral taxane, which may be the same as or different from the first cyclic molecule! /, the second cyclic molecule, and the second cyclic molecule being skewered A second linear molecule that is included in the form of a second linear molecule, which may be the same as or different from the first linear molecule, and the second linear molecule The second cyclic molecule is not detached! / It is a second blocking group disposed at both ends of the second linear molecule, and is different even if it is the same as the first blocking group. Preparing a second poly-oral taxane having a second blocking group The step of:

D) iii) preparing a solvent and iv) a solution having the first solute;

F) i) adding the first poly (oral taxane) and the ii) substance to the solution; and

G) a step of chemically and / or physically cross-linking i) at least a portion of the first polyoral taxane and at least a portion of the ii) substance in the solution to obtain the material;

Have

The effective diffusion coefficient D / q ^{1/3 of} the first solute in the material (D: diffusion coefficient, q: swelling degree of the material) is poly (acrylamide), water, Tris-HCl buffer, and second This is a comparative sample consisting only of disodium 3-hydroxy _4- [(2,4,5-trimethylphenenole) azo] -2,7-naphthalenedisulfonate as a solute of water with a water content of 95%. 1.1 times or more, preferably 1.2 times or more, for example 1.;! To 10 times, preferably 1.2 to 10 times, of the effective diffusion coefficient of the second solute in the comparative sample More preferably 2 to; 10 times, still more preferably 3 to 10 times, most preferably 5 to 10 times.

[0021] <24> In the above 23>, ii) the substance has a) the first polymer, and in step G), at least a part of the first polyoral taxane and at least one of the first polymer in step G). The part should be chemically and / or physically crosslinked.

<25> In step G) of <23> or <24> above, at least a portion of the first poly (taxane) taxane and at least a portion of the first polymer are chemically bonded via a cyclic molecule. It is good to let them.

[0022] <26> In any one of the above <23> to <25>, ii) the substance has b) a second polyrotaxane, and in step G), at least a part of the first polymouth taxane It is preferred to chemically and / or physically cross-link at least a portion of the second polymouth taxane.

<27> In the process G) of any one of the above 23> to 26>, at least a part of the first poly-oral taxane and at least a part of the second poly-oral taxane are bonded via a cyclic molecule. It should be chemically bonded.

[0023] <28> In any one of the above items <18> to <27>, the solvent power S, water, a non-aqueous solvent, and a mixture of water and a non-aqueous solvent may be selected.

<0024> In <29> above 28>, non-aqueous solvent power S, natural oil (for example, glycerin, castor Alcohols (eg methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, etc.); and ethylene glycolanol, diethylene glycolanol, triethylene glycolanol, Polyethylene glycol, tetrapropylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, hexylene glycol, octylene glycol, polyethylene glycol, polypropylene glycol, polyester polyol, etc. Alcohols; fatty acids (especially higher fatty acids such as oleic acid, linolenic acid, etc.); ethers (eg alkyl ethers of polyhydric alcohols, ethylene oxide / propylene oxide copolymers); And a silicone oil (for example, dimethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen silicone oil, etc.) It is preferable to select monoalkyl for polyhydric alcohol alkyl ethers. Whether it is an ether or a polyalkyl ether, mention can be made of the polymethyl alcohols such as monomethyl ether, dimethyl ether, monoethyl ether, and jetyl ether. The molecular weight should be 200 to 600, preferably 200 to 450. Also, for polypropylene glycol (more preferably, the number average molecular weight force is 400 to 5000, more preferably 400 to 3,500).

<30> In any one of the above items 18> to 29>, the weight ratio of the solvent to the poly (or polytaxane) is 1:99 to 99.9: 0.1, preferably 5 : 95-99.9: 0.1, more preferably 10: 90-99.9: 0.1.

<31> In any one of the above items <18> to <30>, the first solute is a gas molecule, acid, base, chloride, iodide, lithium salt, metal ion, polyhydric alcohol, polyethylene glycol, or a derivative thereof. , Lipids, fatty acids, saccharides, amino acids and derivatives thereof, vitamins and derivatives thereof, dye molecules, drug molecules (for example, anti-cancer agents such as anthalacycline anticancer agents actinomycin, dactinomycin, bleomycin, daunomycin, adriamycin Cisplatin and derivatives thereof such as idamycin, mitomycin, and the like, but are not limited to these, and anti-inflammatory agents include, but are not limited to, dexamethasone, indomethacin, menthol, and the like. Lloyd particles, biomolecules (eg tamper Quality, DNA, selected from the group consisting of RNA, etc.) force is also the group consisting of It is better.

[0026] <32> In any one of the above items <18> to <31>, the material strength S, an external medicine (for example, a base material for external application such as an analgesic / anti-inflammatory agent, a base material for skin application, etc.); System carrier materials (eg anti-cancer drug carriers targeting cancer cells); Wound dressings; Water purification agents (eg removers of harmful metals and spoilage odors in swamps, industrial effluents, hot spring water and mine wastewater) Cosmetics (eg gel face mask material, gel cream); cell culture media (eg cell growth media, cell differentiation media, etc.); plant tissue culture media (eg hydroponics); battery electrolytes (eg lithium ion conductivity) Electrolyte material, electrolyte for fuel cell); and selected from the group consisting of contact lenses!

[0027] <33> In any one of the above items <18> to <32>, the first and / or second linear molecule may be polybulal alcohol, polybulurpyrrolidone, poly (meth) acrylic acid, cell port One-year tree-type (canolepoxymethylenoresenorelose, hydroxyethinoresenorelose, hydroxypropyl pill cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polybulacetal resin Polyolefins such as polybutylmethyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, etc. and / or their copolymers, polyethylene, polypropylene, and copolymers of other olefinic monomers Resin, polyester resin, polychlorinated bur resin, polystyrene and acrylic resin Polystyrene resins such as rilonitrile-styrene copolymer resin, acrylic resins such as polymethyl methacrylate and (meth) acrylate copolymers, acrylonitrile methyl acrylate copolymer resins, polycarbonate resins, polyurethane resins, butyl acetate Bure copolymer resins, polybutylpropylar resins, etc .; and derivatives or modified products thereof, polyisobutylene, polytetrahydrofuran, polyadiline, acrylonitrile butadiene styrene copolymer (ABS resin), polyamides such as nylon, polyimide Polyenes such as polyisoprene and polybutadiene, polysiloxanes such as polydimethylsiloxane, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, Riketon acids, Porifue two alkylene ethers, Poriharoore fins such, as well Yogu example polyethylene glycol be selected from the group consisting of derivatives, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol Selected from the group consisting of polyethylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene, and preferably selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene. Polyethylene glycol is particularly good

<34> In any one of the above items <18> to <33>, the first and / or second linear molecule has a molecular weight of 10,000 or more, preferably 20,000 or more, more preferably 3 It should be over 10,000.

<35> In any one of the above items <18> to <34>, the first and / or second blocking group is a dinitrophenyl group, a cyclodextrin, an adamantane group, a trityl group, a fluorescein, a pyrene, Substituted benzenes (Substituents include, but are not limited to, alkyl, alkyloxy, hydroxy, halogen, cyano, sulfonyl, carboxyl, amino, phenyl, etc. One or more substituents may be present. ), Optionally substituted polynuclear aromatics (but not limited to the same as the substituents mentioned above, one or more substituents may be present), and It should be selected from the group consisting of steroids. In addition, it is preferably selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, and pyrenes, more preferably adamantane groups or trityl groups. .

[0029] <36> In any one of the above items <18> to <35>, the first and / or second cyclic molecule may be substituted, or may be a cyclodextrin molecule. ,.

<37> In any one of the above items <18> to <36>, the first and / or second cyclic molecules may be substituted cyclodextrin molecules, and the cyclodextrin molecules are α-cyclodextrin, 13 -It is selected from the group consisting of cyclodextrin, γ-cyclodextrin, and derivatives thereof.

[0030] <38> In any one of the above items <18> to <37>, the first and / or second cyclic molecule may be substituted α-cyclodextrin, and the first and / or second The linear molecule is preferably polyethylene glycol. <39> In any one of the above items <18> to <38>, when the first cyclic molecule is skewered by the first linear molecule, the first cyclic molecule is included to the maximum extent. The amount of the first cyclic molecule is 0.001 -0.6, preferably 0.01 -0.5, and more preferably 0.05 -0.4. It is preferable to be included in a skewered form in a linear molecule. In addition, when the amount of the second cyclic molecule included to the maximum when the second cyclic molecule is skewered by the second linear molecule is 1, the second cyclic molecule is The molecule is skewered by a second linear molecule in an amount of 0.001 -0.6, preferably 0.01 -0.5, more preferably 0.05 -0.4. It is good.

The invention's effect

[0031] According to the present invention, it is possible to provide a material having a high! / Diffusion coefficient, such as a wet gel.

Further, according to the present invention, a material having a high diffusion coefficient and high permeability, for example, wet toggle can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

[0032] Hereinafter, the present invention will be described in detail.

The present invention provides: i) a first poly (oral taxane); ii) the following substances a) and / or b): a) a first polymer other than a poly (oral) taxane; and / or b) a second poly A material having an oral taxane, iii) a solvent, and iv) a first solute; and having a high diffusion coefficient. In the material of the present invention, i) a first polyoral taxane and ii) a substance, that is, a first polymer other than a polyoral taxane; and / or b) a second polyoral taxane, It is preferable that at least a part is crosslinked. The cross-linking is preferably the following cross-linking (i) to (no). That is, a) Cross-linking of poly-oral taxanes (first poly-orth-taxane and second poly-oral-taxane), cross-linking of polymers other than poly-oral taxanes (ie, “first polymer”) and poly-oral taxanes. , ノ,) Cross-linking in which the above ii) and mouth) are present together.

Further, the cross-linking may be chemical cross-linking or physical cross-linking, preferably chemical cross-linking, more preferably chemical cross-linking via a cyclic molecule. Is good.

Hereinafter, the constituent substances contained in the material of the present invention will be described in detail. <0033><Polytaxane>

Each of the first and / or second poly (taxane) taxanes in the present invention seems to be a cyclic molecule, a linear molecule that includes the cyclic molecule in a skewered manner, and a cyclic molecule that does not desorb from the linear molecule. Have blocking groups located at both ends of the linear molecule.

The second polymouth taxane may be the same as or different from the first polymouth taxane. More specifically, the second cyclic molecule may be the same as or different from the first cyclic molecule, and the second linear molecule may be the same as or different from the first linear molecule. The second blocking group may be the same as or different from the first blocking group. Further, the blocking group disposed at one end of the linear molecule may be the same as or different from the blocking group disposed at the other end.

[0034] <Linear molecule of poly (oral taxane)>

In the polymouth taxane of the material of the present invention, the linear molecule is not particularly limited as long as it is a molecule extending in the longitudinal direction, that is, a linear molecule. These linear molecules include poly (vinyl alcohol), poly (pyrrole pyrrolidone), poly (meth) acrylic acid, cellulose resins (such as carboxy methinoresenorelose, hydroxyethinoresenorelose, hydroxypropinoresenorelose), polyacrylamide, Polyethylene oxide, polyethylene glycol, polypropylene glycol, polybulacetal resin, polybulumethyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, etc. and / or copolymers thereof, polyethylene, polypropylene, and others Polyolefin resins such as copolymer resins with polyolefin monomers, polyester resins, polychlorinated bur resins, polystyrene resins such as polystyrene and talylonitrile tristyrene copolymer resins Acrylic resins such as polymethyl methacrylate and (meth) acrylic acid ester copolymer, acrylonitrile methyl acrylate copolymer resin, polycarbonate resin, polyurethane resin, butyl chloride acetate copolymer copolymer, polybutyl pentyl resin, etc .; And derivatives or modified products thereof, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile butadiene styrene copolymer (ABS resin), polyamides such as nylon, polygens such as polyimides, polyisoprene, and polybutadiene. Polysiloxanes such as polydimethylenosiloxane, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins And of these induction Chosen from the group consisting of conductors, but not particularly limited.

For example, it is more preferably selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene, and preferably polyethylene glycol, polypropylene glycol, polytetrahydrofuran, It is particularly preferable to select polyethylene glycol from the group consisting of polydimethylsiloxane, polyethylene, and polypropylene.

[0035] The linear molecule may have a molecular weight of 10,000 or more, preferably 20,000 or more, more preferably 30,000 or more.

[0036] <Polymouth taxane blocking group>

In the polymouth taxane of the material of the present invention, the blocking groups are arranged at both ends of the linear molecule as described above. In addition, the blocking group has an effect that the cyclic molecule is not detached from the linear molecule. There is no particular limitation as long as it is a blocking group having these functions. The blocking groups arranged at both ends of the linear molecule may be the same or different at one end and the other end. As blocking groups, dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes, substituted benzenes (substituents include alkyl, alkyloxy, hydroxy, halogen, cyan, snorfoninore, carboxyl, amino But not limited thereto, one or more substituents may be present), polynuclear aromatics that may be substituted (substituents are the same as those described above) One or more substituents may be present, but not limited thereto.

. ) And steroids. The dinitrophenyl group is preferably selected from the group consisting of cyclodextrins, adamantane groups, trityl groups, fluoresceins, and pyrenes, more preferably adamantane groups or trityl groups. There should be.

<0037> <Polycyclic Taxane Cyclic Molecules>

The cyclic molecule is not particularly limited as long as it is cyclic and takes the above-described state. The cyclic molecule may be an optionally substituted cyclodextrin molecule. The cyclodextrin molecules are α-cyclodextrin, 13-cyclodextrin and γ-cyclodextrin. It may be selected from the group consisting of xistrin and its derivatives.

[0038] In the polymouth taxane of the material of the present invention, the cyclic molecule may be an α-cyclodextrin which may be substituted, and the linear molecule may be polyethylene glycol.

In addition, in the polymouth taxane of the material of the present invention, when the amount of cyclic molecules to be maximally included when the cyclic molecules are skewered by linear molecules is 1, the cyclic molecular force It is preferable to be included in the form of skewers in a linear molecule in an amount of 0.001—0.6, preferably (0,01—0.5, more preferably (0,05—0.4).

[0039] <ii) Substance>

The material of the present invention has ii) a substance in addition to i) the first polyoral taxane. This ii) substance is either a) below, b) or a mixture of a) and b). a) is the first polymer that is other than a polymouth taxane. In addition, b) is a second polymouth taxane that may be the same as or different from the first polymouth taxane.

[0040] <ii) Substance a) First polymer>

The first polymer is a polymer other than the polyoral taxane, and is not particularly limited.

The first polymer) is not particularly limited, but the main chain or side chain is —OH group, NH group

2 It should have at least one selected from the group consisting of a COOH group, an epoxy group, a bur group, a thiol group, and a photocrosslinking group. Examples of the photocrosslinking group include, but are not limited to, cinnamate, coumarin, chalcone, anthracene, styrylpyridine, styrylpyridinium salt, and styrylquinolium salt.

[0041] The first polymer may be a homopolymer or a copolymer. It may have two or more polymers. When it has two or more polymers, it is preferable that at least one polymer is bonded to the polyoral taxane via a cyclic molecule. If the first polymer is a copolymer, it may consist of two, three or more monomer forces. When it is a copolymer, the force S can include, but is not limited to, block copolymers, alternating copolymers, random copolymers, graft copolymers, and the like.

[0042] Examples of the first polymer include polybulal alcohol, polybulurpyrrolidone, poly (meth) acrylic acid, cellulosic resins (carboxymethylcellulose, hydroxyethyl cellulose, hydroxypropylcellulose, etc.), polyacrylamide, polyethylene Oxide, poly Ethylene glycol, polypropylene glycol, polybroacetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, etc. and / or copolymers thereof, polyethylene, polypropylene, and other olefinic monomers Polyolefin resins such as copolymer resins, polyester resins, polychlorinated bur resins, polystyrene resins such as polystyrene and acrylonitrile styrene copolymer resins, polymethyl methacrylate and (meth) acrylate copolymers , Acrylic resins such as acrylonitrile trimethyl acrylate copolymer resin, polycarbonate resin, polyurethane resin, butyl chloride acetate copolymer resin, polybutyl petitral resin, etc .; and derivatives or modified products thereof Polyisobutylene, polytetrahydrofuran, polyaurine, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polyimides, polygenes such as polyisoprene and polybutadiene, polysiloxanes such as polydimethylsiloxane, Forces that can include polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and their derivatives S, these It is not limited to. In addition, as the derivative, the above-described groups, that is, —OH group, —NH group, —COOH group,

2

It is preferable to have at least one selected from the group consisting of an epoxy group, a bur group, a thiol group, and a photocrosslinking group.

[0043] <ii) Substance a) Second poly-oral taxane>

The material of the present invention may have a second polymouth taxane. In this case, the second polymouth taxane may be the same as or different from the first polymouth taxane as described above. The substances constituting the second poly-oral taxane are as described above.

[0044] <Solvent>

In the present invention, the solvent may be selected from the group consisting of water, a non-aqueous solvent, and a mixture of water and a non-aqueous solvent.

The non-aqueous solvent refers to a liquid other than water, and may be a single liquid or a mixture of a plurality of liquids. The non-aqueous solvent is preferably a liquid at room temperature from the viewpoint of handling and the like. However, depending on the use of the material of the present invention, a temperature exceeding room temperature (for example, 50 to 200 ° C.), a temperature not exceeding the room temperature! /, Use liquid form (eg 140 to 0 ° C) That's it.

[0045] As non-aqueous solvents, natural oils (eg, glycerin, castor oil, olive oil, etc.); alcohols (eg, methanolol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol) Monohydric alcohols such as; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, hexylene glycol, Fatty acids (especially higher fatty acids, such as oleic acid, linolenic acid, etc.); ethers (eg, alkyl ethers of polyhydric alcohols), such as octylene glycol, polyethylene glycol, polypropylene glycol, polyester polyols; Selected from the group consisting of ethyl ether, propylene oxide copolymer, etc .; ethyl abietate; and silicone oil (eg, dimethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen silicone oil, etc.) However, the alkyl ethers of polyhydric alcohols may be mono-alkylene ethers or polyalkyl ethers, polyhydric alcohol mono-methyloate or dimethinoleate. Tenole, monoethinoreethenore, jetinoreethenore, etc. Polyethylene glycol has a number average molecular weight of 200 to 600, preferably 200 to 450. For glycols, number average molecular weight 400 to 5000, more is preferably (or 400 to 3,500 mosquitoes Yo Rere.

[0046] The amount of the solvent is preferably in the following range. That is, the weight ratio of the solvent to the poly (or polytaxane) (solvent: poly (or polytaxane)) 1:99 to 99.9: 0.1, preferably (or 5:95 to 99.9: 0.1, more preferably Should be between 10:90 and 99.9: 0.1.

[0047] <First solute>

In the present invention, the first solute is a solute having a high diffusion coefficient in the material of the present invention. The first solute of the present invention is not particularly limited, but examples thereof include gas molecules, acids, bases, chlorides, iodides, lithium salts, metal ions, polyhydric alcohols, polyethylene dallicol and derivatives thereof, lipids, fatty acids, Saccharides, amino acids and derivatives thereof, vitamins and derivatives thereof, dye molecules, drug molecules (for example, anti-cancer drugs such as antatincycline anti-cancer chiral Ij actinomycin, dactinomycin, bleomycin, daunomycin, Examples include, but are not limited to, cisplatin and its derivatives such as adriamycin, idamycin, and mitomycin. Examples of anti-inflammatory agents include, but are not limited to, dexamethasone, indomethacin, menthol and the like. ), Colloidal particles, and biomolecules (eg, protein, DNA, RNA, etc.) force.

[0048] Note that the solvent may contain a solute other than the first solute that does not substantially affect the effective diffusion coefficient of the material. For example, pH adjusters (buffering agents), cationic surfactants, aionic surfactants, noionic surfactants, antioxidants, heat stabilizers, UV absorbers, bactericides, pigments, colorants, fragrances However, it is not limited to these.

[0049] <Effective diffusion coefficient>

The material of the present invention has a high! / Effective diffusion coefficient D / q ^1/3 (D: diffusion coefficient, q: degree of swelling of the material) compared with the comparative sample.

In this specification, comparative samples are poly (acrylamide), water, and disodium 3-hydroxy _4- [(2,4,5-trimethylphenenole) azo] -2,7- as the second solute. It consists only of naphthalenedisulfonate r (Disodium j-hydroxy-4-[(2,4,5-tnmethylphenyl) azo] -2,7-naphthaienedisulfonate). Here, disodium 3_hydroxy _4_ [(2,4,5_trimethylphenyl) azo] -2,7-naphthalenedisulfonate is the general name S “Ponceau 3R” Red It is a pigment.

[0050] In the present invention, a comparative sample obtained by the method described in Non-Patent Document 1 is used.

That is, acrylamide and N, N, -methylenebisacrylamide (crosslinking agent) were dissolved in 100 ml of distilled water to obtain a solution containing 693 mM acrylamide and 7 mM N, N, -methylenebisacrylamide. To this solution, Ν, Ν, Ν ', Ν'-tetramethylethylenediamine was added as an accelerator and stirred for 20 minutes. The gel holder was immersed in this pregel solution and degassed for 30 minutes. To the pregel solution, 4 ml of ammonium persulfate (ml) (initiator) was added to initiate the polymerization, and left at 20 ° C for 1 day, disodium 3-hydroxy -4--[(2,4 , 5-trimethylphenyl) azo] -2,7-naphthalenedisulfonate! /, Comparative test I got a fee.

[0051] The water content of the comparative sample is 95 wt%.

In this specification, the water content of the comparative sample is the following formula when the weight of water and poly (acrylamide) and force is Wx and the weight of poly (acrylamide) is Wy. You can express yourself.

[0052] (Water content of comparative sample, wt%) = (Wx-Wy) / Wx X lOO

[0053] The degree of swelling can be determined by the following equation.

[0054] (Swelling degree of comparison sample, q ′)

[0055] The diffusion coefficient D 'of the second solute (disodium 3-hydroxy_4-[(2,4,5-trimethylphenyl) azo] -2,7-naphthalenedisulfonate) in this comparative sample is Measured by the time lag method using side-by-side cells (see Non-Patent Document 1 and see the examples below). From the above q ', the effective diffusion coefficient D' / q ^{1 / 3} is calculated.

On the other hand, the effective diffusion coefficient of the material of the present invention is measured as follows.

(Swelling degree of the material of the present invention q) = wl / w2

Where wl is the weight of the gel swollen to the equilibrium state in the solvent (ie i) the first polyrotaxane; ii) the substance; and iii) the solvent; and w2 is after the solvent has been removed. It is the weight of dry genolet (ie, wl minus iii) solvent).

[0057] The diffusion coefficient D of the first solute of the material of the present invention having the first solute and the solvent is measured using the same apparatus as that for measuring D 'of the comparative sample. From these D and q, the effective diffusion coefficient D / q ^1/3 of the present invention is calculated.

The effective diffusion coefficient D / q ^1/3 in the present invention is 1.1 times or more, preferably 1.2 times or more, for example 1.;! To 10 times the effective diffusion coefficient D ′ / q ^1/3 of the comparative sample. , Preferably 1.2 to 10 times, more preferably 2 to 10 times, still more preferably 3 to 10 times, most preferably 5 to 10 times.

The material of the present invention can be used in fields where a high diffusion coefficient is desired. For example, the material of the present invention is not particularly limited, but is an external medicine (for example, a base material for external application such as an analgesic / anti-inflammatory agent, a base material for skin application); a carrier material for a drug delivery system (for example, Anticancer drug carrier targeting cancer cells); Wound dressing; Water purification agent (for example, removal of harmful metals and rot odor in marsh, factory effluent, hot spring water and mine wastewater); Cosmetics (for example, gel-like) Face mask material, gel cream); Cell culture medium (eg cell propagation medium, cell differentiation medium, etc.); Plant tissue culture medium (eg hydroponic culture, etc.); Battery electrolyte (eg lithium ion conductive electrolyte material, fuel) Electrolytes for batteries); and selected from the group consisting of contact lenses!

[0059] <Method for producing material of the present invention, part 1>

The material of the present invention described above can be manufactured, for example, as follows.

A) the first cyclic molecule, the first linear molecule that includes the first cyclic molecule in a skewered manner, and the first cyclic molecule so as not to be detached from the first linear molecule. Preparing a first poly-ortaxane having a first blocking group disposed at both ends of the first linear molecule;

B) The following steps a ′) and / or): ii) preparing the substance,

a ') providing a first polymer; or

b ′) a step for preparing a second poly-taxane, which may be the same as or different from the first cyclic molecule! /, the second cyclic molecule, and the second cyclic molecule being skewered A second linear molecule that is included in the form of a second linear molecule, which may be the same as or different from the first linear molecule, and the second linear molecule The second cyclic molecule is not detached! / It is a second blocking group disposed at both ends of the second linear molecule, and is different even if it is the same as the first blocking group. Providing a second polymouth taxane having an optional second blocking group;

D) preparing a solution having said iii) solvent and iv) a first solute; and

E) obtaining the material by bringing the cross-linked poly (oral taxane) into contact with the solution;

[0060] In this production method, as described above, the cross-linking between i) at least part of the first polyoral taxane in step C) and at least part of the substance ii) is as follows: It is good that it is bridge | crosslinking. I) Poly-polytaxanes (cross-linking of the first poly-and-taxane and the second poly-mouth taxane), cross-linking of polymers other than polyrotaxane (ie, “first polymer”) and the poly-polytaxane, and the above Ii) and mouth) exist together.

In this production method, the above-mentioned ones can be used as the polymouth taxane, the solvent, the first solute, and the like. In addition, the above-mentioned polymers can be used as the polymer other than the polyditaxane, that is, the “first polymer”.

In addition, the above-described material of the present invention can be manufactured as follows, for example.

That is, A) the first cyclic molecule, the first linear molecule that includes the first cyclic molecule in a skewered manner, and the first cyclic molecule so as not to be detached from the first linear molecule. Preparing a first poly-ortaxane having a first blocking group disposed at both ends of the first linear molecule;

B) by the following steps a ′) and / or b ′), ii) preparing the substance,

a ′) providing a first polymer or precursor thereof; or

D) iii) preparing a solvent and iv) a solution having the first solute;

G) a step of chemically and / or physically cross-linking i) at least a portion of the first polyoral taxane and at least a portion of the ii) substance in the solution to obtain the material; You can get the power S by having S.

[0062] In this production method, the crosslinking in step G) is the same as in step C). Examples of the crosslinking in step G) include, but are not limited to, thermal crosslinking and photocrosslinking.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1

Hydropropylated poly-oral taxane HAPR (linear molecule: polyethylene glycol (molecular weight: 350,000), cyclic molecule: a-cyclodextrin, inclusion amount of a-cyclodextrin: 26%, blocking group: Damantanamine, hydroxypropylation rate: 47.5% vs. OH group) 2.5 g was dissolved in 10 mL of 0.01 N NaOH aqueous solution. The crosslinker divinyl sulfone DVS 150 1 (0.177 g) was added to the above aqueous solution. Hydroxypropylated polyrotaxane HAPR was obtained by a method similar to the method described in WO2005 / 080469 (the contents of this document are all incorporated herein). The reaction was carried out at 5 ° C. for 24 hours to obtain a crosslinked hydroxypropylated polyortaxane A-1. The obtained crosslinked hydroxypropylated poly (oral taxane) A-1 was immersed in pure water to swell. The surrounding pure water was changed repeatedly and swollen until equilibrium was reached.

The weight wl of the cross-linked hydroxypropylated polymouth taxane A-1 in the swelling equilibrium was 0.45 27 g. On the other hand, the weight w2 of the A-1 alone was determined by vacuum drying the cross-linked hydroxypropylated polyortaxane A-1 at room temperature for 2 days, resulting in 0.0435 g. From these wl and w2, the degree of swelling q (q = wl / w2) of the crosslinked hydroxypropylated polyortaxane A— 1 is 10, and the water content (((wl—w2) / wl) X 100 ( wt%)) was 90 wt%.

[0065] <Measurement of Diffusion Coefficient of Substance in Cross-linked Hydroxypropylated Poly-Taxane A-1>

Using the side-by-side cell 1 shown schematically in Fig. 1 (in fact, a side-by-side cell manufactured by Perme Gear was used), the diffusion coefficient of the substance in the cross-linked hydroxypropylated polymouth taxane A-1 was measured. . As a substance, disodium 3-hydroxy-4-[(2,4,5-tri Methylphenyl) azo] -2,7-naphthalenedisulfonate (generic name “Ponceau 3R”, hereinafter abbreviated as “Bonso 3R”) Experiment).

First, the cross-linked hydroxypropylated poly-ortaxane A-1 (“4” in FIG. 1) was fixed between two cells (in FIG. 1, the left cell was “2” and the right cell was “3”).

The left cell 2 has Ponso 3R as a solute (schematically indicated by “6” in FIG. 1) and Tris-hydrochloric acid buffer (ρΗ6 · 9) as a solvent (schematically indicated by “7” in FIG. 1). 8 mL of aqueous solution was injected.

In the right cell 3, 8 mL of only Tris-hydrochloric acid buffer (pH 6.9) (schematically indicated by “7” in FIG. 1) used as a solvent in the left cell 2 was injected.

Time-dependent change in absorbance of Poncoso 3R that permeated through the cross-linked hydroxypropylated poly (R) taxane A-1 ("4" in Fig. 1) (permeation direction: "A" in Fig. 1) and diffused into the right cell 3 Was measured using an ultraviolet visible spectrophotometer AGILENT 8453 (manufactured by Agilent Technologies).

Figure 2 shows the measurement results. FIG. 2 is a diagram showing the time change of the absorbance of Poncoso 3R in the right cell 3. In Fig. 2, ♦, country, and ▲ are the values when the starting concentration of Poncoso 3R in left cell 2 is 4 mmol / L (+), 8 mmol / L (garden), and 12 mmol / L (A), respectively. Results are shown.

After some time at any starting concentration, Poncoso 3R was detected in the right cell. This detection start time (time lag) was constant regardless of the start concentration. Time lag t and

L

From the measurement result of gel thickness d, the diffusion coefficient D of Ponceau 3R in cross-linked hydroxypropylated poly-ortaxane A-1 was determined according to the following formula (time lag method), and it was 1.88 X 10 ms. .

[0066] [Equation 1]

D

6 t, Example 2

[0067] <Preparation of Crosslinked Hydroxypropylated Poly Mouth Taxane A-2> A crosslinked hydroxypropylated polyortaxane A-2 was obtained in the same manner as in Example 1 except that the amount of the crosslinking agent divinylsulfone DVS was changed to 50 1 (0 · 059 g). The obtained cross-linked hydroxypropylated poly (oral taxane) A-2 was immersed in pure water and swollen in the same manner as in Example 1. The degree of swelling q (q = wl / w2) of the cross-linked hydroxypropylated poly-ortaxane A-2 was 18, and the water content was 94 wt%.

[0068] <Diffusion Coefficient of Crosslinked Hydroxypropylated Poly Mouth Taxane A-2>

In addition, when the diffusion coefficient of Poncoso 3R in the crosslinked hydroxypropylated polyortaxane A-2 was determined by the same method as in Example 1, it was 3.33 X ^{10 — 1 ()} m ² / s.

Example 3

[0069] <Preparation of Crosslinked Hydroxypropylated Poly Mouth Taxane A-3>

By the same method as in Example 1 except that the amount of the crosslinking agent divinylsulfone DVS was changed to 250 1 (0 · 295 g), a crosslinked hydroxypropylated polyortaxane A-3 was obtained. The obtained crosslinked hydroxypropylated poly (oral taxane) A-3 was immersed in pure water and swollen in the same manner as in Example 1. The degree of swelling q (q = wl / w2) of the cross-linked hydroxypropylated polyortaxane A-3 was 6, and the water content was 83 wt%.

[0070] <Diffusion Coefficient of Crosslinked Hydroxypropylated Poly Mouth Taxane A-3>

In addition, when the diffusion coefficient of Poncoso 3R in the crosslinked hydroxypropylated polyortaxane A-3 was determined by the same method as in Example 1, it was 0.78 X ^{10 — 1 ()} m ² / s.

[0071] (Comparative Example 1)

Tokita is a Tokita, M., Jpn. J. Appl. Phys. 34, 2418-2422 (1995) measurement of the diffusion coefficient of Poncoso 3R in polyatrylamide gel (water content: 95%, thickness: approx. Lmm). Is described. Here, the measurement was performed under exactly the same conditions as in Example 1, that is, using the same time lag method under the same measurement conditions (the buffer solution was Tris-hydrochloric acid buffer (ρΗ6 · 9)). The result was 0.98 X 10-1 ⁽⁾ m ² / s.

Polyacrylamide was obtained by the same method as in Non-Patent Document 1, as described above.

[0072] The results of Examples;! To 3 and Comparative Example 1 are shown in Table 1. Table 1 describes the effective diffusion coefficient D Zq.

Table 1 shows the following. That is, compared with Example 2 (water content 94%), which has almost the same water content Comparing Example 1 (water content 95%), it can be seen that the diffusion coefficient of Poncoso 3R in A-2 of Example 2 was about 3 times or more larger than that of the polyacrylamide gel of Comparative Example 1. The diffusion coefficient (1.88) of Example 1 (water content 90%), which is lower than that of Comparative Example 1 (water content 95%), is about twice as large as that of Comparative Example 1 (0 · 98). You can see what happened.

It can be seen that Example 3 (water content 83%) has a slightly smaller diffusion coefficient than Comparative Example 1 (water content 95%).

From these results, comparing the present invention with Comparative Example 1, it can be seen that when the water content is the same, the material of the present invention quickly diffuses the ponso 3R. This is thought to be because the network chain of cross-linked polymouth taxis has a more flexible structure than chemical gels, and the restriction on diffusion is reduced.

[0073] The following can be seen from the results of Examples 1 to 3.

As the degree of swelling of the gel material increases, the diffusion coefficient of the solute therein increases. In general, diffusion of solutes in gel materials tends to increase as the mesh size of the material increases. The mesh size of the gel material is proportional to the 1/3 power (q ^1/3 ) of the degree of swelling q. That is, q ^1/3 is directly related to the diffusion coefficient of the solute. In order to effectively compare the diffusivities of gel materials with different degrees of swelling, evaluation was made using an effective diffusion coefficient of D / q ^1/3 (D: diffusion coefficient, q ^1/3 : degree of swelling). Do it! /

Comparing Example 3 (q = 6) and Comparative Example l (q = 20), the present invention is a material having a high effective diffusion coefficient, that is, a high diffusivity even when the degree of swelling is low and the water content is low. The ability to provide

In addition, when Example 2 and Comparative Example 1 are compared, it can be seen that the present invention can provide a material having an effective diffusion coefficient of about 3.5 times when the degree of swelling and moisture content are the same. .

[0074] [Table 1] Table 1. Characteristics of Example 1-· "3 and Comparative Example 1 Example 1 Example 2 Example 3 Comparative Example 1 Swelling degree g 1 0 1 8 6 2 0 Moisture content u (wt%) 9 0 94 8 3 9 5 Diffusion coefficient D

1. 8 8 3. 3 3 0. 7 8 0. 9 8

(XlO-'V / s) Effective diffusion coefficient

O / g ^1/3 8. 7 3 1 2. 7 4. 2 9 3. 6 1

(X10- ⁿ m ² / s)

Brief Description of Drawings

1] In the present invention, it is a diagram showing an outline of a side-by-side cell for measuring a diffusion coefficient.

FIG. 2 shows the experimental results of Example 1.

Claims

The scope of the claims

[1] i) a first polymouth taxane,

ii) the following substances a) and / or b):

a) a first polymer that is other than a polymouth taxane;

b) a second polymouth taxane,

iii) solvent, and

iv) the first solute;

A material having

The effective diffusion coefficient D / q ^{1/3 of} the first solute in the material (D: diffusion coefficient, q: swelling degree of the material) is poly (acrylamide), water, Tris-HCl buffer, and second This is a comparative sample consisting only of disodium 3-hydroxy _4- [(2,4,5-trimethylphenenole) azo] -2,7-naphthalenedisulfonate as a solute of water with a water content of 95%. The above material, which is 1.1 times or more the effective diffusion coefficient of the second solute in the comparative sample.

[2] The substance ii) includes: a) a first polymer, and at least a part of the first polyoral taxane and

The material according to claim 1, wherein at least a part of one polymer is chemically and / or physically crosslinked.

[3] At least part of the first poly-oral taxane and at least part of the first polymer are cyclic The material according to claim 1 or 2, which is chemically bonded via a molecule.

[4] The substance ii) has b) a second polymouth taxane, and at least part of the first polymouth taxane and at least part of the second polymouth taxane are chemically and / or physical. The material according to any one of claims 1 to 3.

[5] The method according to any one of claims 1 to 4, wherein at least a part of the first polyoral taxane and at least a part of the second polyoral taxane are chemically bonded via a cyclic molecule; material.

6. The material according to any one of claims 1 to 5, wherein the solvent is selected from the group consisting of water, a non-aqueous solvent, and a mixture of water and a non-aqueous solvent.

7. The material according to claim 6, wherein the non-aqueous solvent is selected from the group consisting of natural oils, alcohols, fatty acids, ethers, ethyl abietic acid, and silicone oils.

[8] The weight ratio of the solvent and the poly (oral) taxane (solvent: poly (oral) taxane) is 1:99 to 99.9.

The material according to any one of claims 1 to 7, which is 0.1.

[9] The first solute is a gas molecule, acid, base, chloride, iodide, lithium salt, metal ion, polyhydric alcohol, polyethylene glycol and its derivatives, lipid, fatty acid, saccharide, amino acid and its The material according to any one of claims 1 to 8, which is selected from the group consisting of derivatives, vitamins and derivatives thereof, pigment molecules, drug molecules, colloidal particles, and biomolecules.

[10] The material is an external medicine; a carrier material for a drug delivery system; a wound dressing; a water purification agent

10. A cosmetic material; a cell culture medium; a plant tissue culture medium; a battery electrolyte; and a group power consisting of a contact lens;

[11] The first and / or second linear molecule is selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene. Claims !! ~ 10! /, Material according to claim 1.

12. The first and / or second linear molecule has a molecular weight of 10,000 or more.

~; 11! /, The material according to item 1.

[13] The first and / or second blocking group is replaced with dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes, substituted benzenes, Claims selected from the group consisting of Moyo! /, Polynuclear aromatics, and steroids Any force of! To 12, the material according to item 1;

[14] The material according to any one of [1] to [13], wherein the first and / or second cyclic molecule is substituted and may be a cyclodextrin molecule.

[15] The first and / or the second cyclic molecule may be substituted and may be a cyclodextrin molecule, and the cyclodextrin molecule may be α-cyclodextrin, 0-cyclodextrin and γ- Claims 1-1 selected from the group consisting of cyclodextrins and derivatives thereof

5. The material according to any one of 4 above.

[16] The claim wherein the first and / or second cyclic molecule is optionally substituted α-cyclodextrin, and the first and / or second linear molecule is polyethylene glycol. Item;! ~ 15! /, The material according to item 1.

[17] When the first cyclic molecule is clasped by the first linear molecule in a skewered manner, the maximum amount of inclusion of the first cyclic molecule is 1. 1 cyclic molecule is 0.00;! ~ 0.

In the case where the first linear molecule is included in a skewered manner in an amount of 6 and has a second polymouth taxane, the second cyclic molecule is included in a skewered manner by the second linear molecule. When the maximum amount of inclusion of the second cyclic molecule is 1, the second cyclic molecule is 0.00;

The material according to any one of claims 1 to 16, which is skewered by the second linear molecule in an amount of 0.6.

[18] i) the first polymouth taxane,

ii) the following substances a) and / or b):

a) a first polymer that is other than a polymouth taxane;

b) a second polymouth taxane,

iii) solvent, and

iv) a method for producing a material having a first solute;

B) The following steps a ′) and / or): ii) preparing the substance,

a ') preparing a first polymer; or b ') a step of preparing a second poly-ortaxane, which may be the same as or different from the first cyclic molecule! /, the second cyclic molecule and the second cyclic molecule are skewered A second linear molecule that is included in the form of a second linear molecule that may be the same as or different from the first linear molecule, and the second linear molecule A second blocking group disposed at both ends of the second linear molecule so that the second cyclic molecule does not leave, and it may be the same as or different from the first blocking group. Providing a second polymouth taxane having a good second blocking group;

D) preparing a solution having said iii) solvent and iv) a first solute; and

The effective diffusion coefficient D / q ^{1/3 of} the first solute in the material (D: diffusion coefficient, q: swelling degree of the material) is poly (acrylamide), water, Tris-HCl buffer, and second This is a comparative sample consisting only of disodium 3-hydroxy _4-[(2,4,5-trimethylphenol) azo] -2,7-naphthalenedisulfonate as a solute of water with a water content of 95%. The above method, wherein the effective diffusion coefficient of the second solute in the comparative sample is 1.1 times or more.

[19] The substance ii) has a) the first polymer, and in the step C), at least part of the first polyrotaxane and at least part of the first polymer are chemically and / or physically The method according to claim 18, which is specifically crosslinked.

[20] The method according to claim 18 or 19, wherein in the step C), at least a part of the first poly (oral taxane) and at least a part of the first polymer are chemically bonded via a cyclic molecule. Method.

[21] The substance ii) has b) a second polyortaxane, and in the step C), at least a part of the first polyrotaxane and at least a part of the second polyortaxane are chemically treated. 21. A method according to any one of claims 18 to 20, wherein the method is physically crosslinked.

[22] The method according to any one of claims 18 to 21, wherein in the step C), at least a part of the first polyoral taxane and at least a part of the second polyoral taxane are chemically bonded via a cyclic molecule. Z Any one of the methods according to 1.

i) the first poly oral taxane,

ii) the following substances a) and / or b):

a) a first polymer that is other than a polymouth taxane;

b) a second polymouth taxane,

iii) solvent, and

iv) a method for producing a material having a first solute;

B) The following steps a ′) and / or): ii) preparing the substance,

a ′) providing a first polymer or precursor thereof; or

D) preparing a solution having the iii) solvent and iv) the first solute;

F) adding i) the first polymouth taxane and ii) the substance to the solution; and

G) a step of i) chemically and / or physically cross-linking at least a part of the first polyoral taxane and at least a part of the substance in the solution to obtain the material;

Have

The effective diffusion coefficient D / q ^{1/3 of} the first solute in the material (D: diffusion coefficient, q: swelling degree of the material) is poly (acrylamide), water, Tris-HCl buffer, and second This is a comparative sample consisting only of disodium 3-hydroxy _4-[(2,4,5-trimethylphenol) azo] -2,7-naphthalenedisulfonate as a solute of water with a water content of 95%. To the comparative sample The above method, wherein the effective diffusion coefficient of the second solute is 1.1 times or more.

[24] The substance ii) has a) the first polymer, and in step G), at least a part of the first polyrotaxane and at least a part of the first polymer are chemically and / or physically 24. The method of claim 23, wherein the method is specifically crosslinked.

[25] The method according to claim 23 or 24, wherein, in the step G), at least a part of the first poly (oral taxane) and at least a part of the first polymer are chemically bonded via a cyclic molecule. Method.

[26] The substance ii) has b) a second polyortaxane, and in step G), at least a part of the first polyrotaxane and at least a part of the second polyortaxane are chemically treated. 26. A method according to any one of claims 23 to 25, wherein the method is and / or physically crosslinked.

[27] The method according to any one of [23] to [26], wherein in step G), at least a part of the first poly-oral taxane and at least a part of the second poly-oral taxane are chemically bonded via a cyclic molecule. Method.