WO2007026886A1 - Polymer blend of polyrotaxane and use thereof - Google Patents

Polymer blend of polyrotaxane and use thereof Download PDF

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Publication number
WO2007026886A1
WO2007026886A1 PCT/JP2006/317363 JP2006317363W WO2007026886A1 WO 2007026886 A1 WO2007026886 A1 WO 2007026886A1 JP 2006317363 W JP2006317363 W JP 2006317363W WO 2007026886 A1 WO2007026886 A1 WO 2007026886A1
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component
polymer blend
polymer
taxane
group
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PCT/JP2006/317363
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French (fr)
Japanese (ja)
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Kohzo Ito
Jun Araki
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The University Of Tokyo
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • C08B37/0015Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/16Cyclodextrin; Derivatives thereof
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/96Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/16Halogen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/20Carboxylic acid amides

Definitions

  • the present invention relates to a polymer blend of a novel polyortaxane and a molded article containing the polymer blend.
  • Polymouth taxanes are pseudo molecules in which the opening of a cyclic molecule (rotator) is pierced by a linear molecule (axis), and the cyclic molecule includes the linear molecule. Blocking groups are arranged at both ends of the polyrotaxane (both ends of the linear molecule) so that the cyclic molecule is not released.
  • ⁇ -cyclodextrin as a cyclic molecule hereinafter, cyclodextrin may be simply abbreviated as “CD”) and polyethylene glycol as a linear molecule (hereinafter sometimes abbreviated as “PEG”) (See, for example, Patent Document 1), and these have been actively applied in recent years.
  • Patent Document 1 Japanese Patent No. 2810264
  • Non-patent literature l Harada, A .; Li, J .; Kamachi, M. Macromolecules 1990, 23, 2821-2823
  • Non-patent literature 2 Harada, A .; Li, J .; Kamachi, M. Nature 1992, 356,325 -327
  • Non-Patent Document 3 Harada, A .; Li, J .; Kamachi, M. Nature 1993, 364, 516-518 Disclosure of the Invention
  • An object of the present invention is to provide a polymer blend that is a polymouth taxane and other polymer materials. It is to provide and to provide a molded article comprising this polymer blend. Means for solving the problem
  • tertiary amine oxides or their hydrates, amides and halogenated metals, and ionic liquids are good solvents for polyoral taxanes, and other polymeric materials and polymers that can be dissolved therein.
  • tertiary amine oxides or their hydrates, amides and halogenated metals, and ionic liquids are good solvents for polyoral taxanes, and other polymeric materials and polymers that can be dissolved therein.
  • the present invention is selected from the group consisting of (1) a polyoral taxane, and (2) (a) a tertiary amine oxide or a hydrate thereof; an amide and a halogenated metal; and an ionic liquid force.
  • the present invention relates to a polymer blend that also has a polymer material power that can be dissolved in at least one solvent.
  • the present invention also relates to a molded article such as a fiber or film containing the polymer blend. The invention's effect
  • polypolytaxane and other polymer material strength properties derived from the polymouthtaxane (strength, elasticity, water absorption or (E.g., growth) can be newly added, and the utility value is high.
  • properties derived from the polymouthtaxane can be newly added, and the utility value is high.
  • the above-mentioned properties can be remarkably improved by crosslinking the poly (taxane) taxane.
  • crosslinking the poly (taxane) taxane By using this, it becomes possible to obtain a material having unprecedented physical properties.
  • the polyblend taxane of the present invention and other polymer blends having high polymer materials can be easily formed into molded articles such as fibers and films, and are highly useful.
  • FIG. 1 is a photomicrograph of fibers obtained using a solution containing a poly (taxane) taxane prepared from the solution (1) and the solution (2) of Example 3 at a volume ratio of 1: 2.
  • the polyortaxane refers to a quasi-polyrotaxane in which openings of a cyclic molecule are pierced by linear molecules and the cyclic molecules include the linear molecules (both linear molecules).
  • a linear molecule is a molecule or substance that is included in a cyclic molecule and can be integrated non-covalently, and is not particularly limited as long as it is linear. Any molecule, including molecules, may be used.
  • linear of “linear molecule” means substantially “linear”. That is, the linear molecule may have a branched chain as long as the cyclic molecule as a rotor is rotatable or the cyclic molecule is slidable or movable on the linear molecule. Further, the length of the “linear” is not particularly limited as long as the cyclic molecule can slide or move on the linear molecule.
  • the “straight chain” of the “linear molecule” is relatively determined depending on the relationship with the polymouth taxane material.
  • the linear molecule may be only a part in the material. Even if it is only a small part, the length is not particularly limited as long as the cyclic molecule can slide or move on the linear molecule as described above.
  • both a hydrophilic polymer and a hydrophobic polymer can be used.
  • the hydrophilic polymer include polybutanol, polypyrrole pyrrolidone, poly (meth) acrylic acid, cellulose-based resin (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc.), polyacrylamide, polyethyleneoxide, polyethylene.
  • Examples include glycols, polybulacetal resin, polybulumethyl ether, polyamines, polyethyleneimine, casein, gelatin, starch, and Z or copolymers thereof;
  • examples of hydrophobic polymers include Polyolefin, polypropylene, and other polyolefin resins such as copolymer resins, polyester resins, polychlorinated butadiene resins, polystyrene and acrylonitrile-styrene copolymers such as styrene copolymer resins
  • Acrylic resins such as tyrene-based resin, polymethylmetatalylate, (meth) acrylate copolymer, acrylonitrile methyl acrylate copolymer resin, polycarbonate resin, polyurethane resin, salt resin Examples thereof include vinyl copolymer resin, polyvinyl butyral resin, etc .; and derivatives or modified products thereof.
  • Polysiloxanes such as polysulfones, polysulfines, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and derivatives thereof should also be used Can do.
  • polyethylene glycol polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene are preferable. Particularly preferred is polyethylene glycol.
  • the linear molecule should have a number average molecular weight of 1,000 or more, for example, 1,000-1, 000, 000. More preferably, 5,000 or more, 5,000 to 1,000,000 or 5,000 to 500,000, even more preferable ⁇ is 10,000 or more, for example, 10,000 to 1,000,000 10,000 to 500,000 or 10,000 to 300,000.
  • the linear molecule preferably has reactive groups at both ends. By having a reactive group, it can easily react with a blocking group. Examples of reactive groups include forces that depend on the block group used, such as hydroxyl groups, amino groups, carboxyl groups, and thiol groups.
  • Examples of the cyclic molecule include various cyclodextrins, for example, unmodified cyclodextrins such as ⁇ -cyclodextrin, ⁇ -cyclodextrin, and ⁇ -cyclodextrin.
  • unmodified cyclodextrins such as ⁇ -cyclodextrin, ⁇ -cyclodextrin, and ⁇ -cyclodextrin.
  • a polyoral taxane whose cyclic molecule is a cyclodextrin is particularly insoluble and has few good solvents. This insolubility is thought to be because the hydroxyl groups present on the cyclodextrin form intramolecular and intermolecular hydrogen bonds, but the detailed mechanism is unknown.
  • cyclodextrins are dimethyl cyclodextrins, hydroxypropyl cyclodextrins, hydroxyethyl cyclodextrin, acetyl cycloalkyl cyclodextrins, etc., which have partially modified hydroxyl groups.
  • the above cyclodextrins have different sizes of the opening of the cyclic molecule depending on the type. Therefore, the type of linear molecule to be used, specifically, when the linear molecule to be used is assumed to be cylindrical, the cyclic molecule to be used depends on the diameter of the cross section of the cylinder, the hydrophobicity or hydrophilicity of the linear molecule, etc. Can be selected. Also, cyclic molecules with relatively large openings When using a cylindrical linear molecule with a relatively small diameter,
  • Two or more linear molecules can be included.
  • the blocking group is not particularly limited as long as it is a group that retains a form in which a cyclic molecule is skewered by a linear molecule, and any group may be used.
  • examples of such a group include a group having “bulkiness” and a group having Z or “ionicity”.
  • the “group” means various groups including a molecular group and a polymer group. That is, the group having “bulkyness” may be a group that is schematically represented by a sphere or a solid support represented by a side wall.
  • the “ionicity” of the group having “ionicity” and the “ionicity” of the cyclic molecule influence each other, for example, by repulsion, the cyclic molecule is skewered by a linear molecule. It is possible to retain the form.
  • the blocking group may be a polymer main chain or a side chain as long as it retains a skewered shape as described above.
  • the blocking group is polymer A
  • a form in which polymer A is partially contained may be used.
  • a composite material having a combination of the properties of the polymouth taxane material and the properties of the polymer A can be formed.
  • Examples of the blocking group include 2,4-dinitrophenyl group, 3,5-dinitrophenyl group and other di-trophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, and pyrene. And derivatives or modified products thereof.
  • cyclodextrin 2, 4-di-trifluoro group as a blocking group
  • di-trifluoro groups such as 3,5-di-phenol groups, adamantane groups, trityl groups, fluoresceins and pyrenes, and derivatives or modified products thereof.
  • the amount of the cyclic molecule penetrating in a straight chain molecule it is preferable to control the amount of the cyclic molecule penetrating in a straight chain molecule. It is preferable that at least two cyclic molecules are pierced with linear molecules, and at least two cyclic molecules include the linear molecules. In addition, the ring segment When the maximum amount of a molecule can be present on a linear molecule, that is, when the maximum inclusion amount is 1, the amount of cyclic molecules is 0.001 to 0.6, preferably the maximum inclusion amount. It is preferably present at a value of 0.01 to 0.5, more preferably 0.05 to 0.4.
  • polypolytaxanes have cyclodextrins, in particular (X-cyclodextrinca, pseudopolyrotaxane clathrating polyethylene glycol with blocking groups (adamantane groups, ditophole groups, etc.). Polymouth taxane.
  • the component (2) is a polymer material that can be dissolved in at least one solvent selected from the group consisting of (a) tertiary amine oxides or hydrates thereof; amides and halogenated metals; and ionic liquid forces. is there.
  • the polymer material does not contain the component (1).
  • the component (a) is a solvent that can also dissolve the component (1), and can function as a common solvent for the components (1) and (2).
  • the component (a) is a solid at room temperature, but includes those that exhibit fluidity by heating, preferably 40 to 150 ° C., and can function as a solvent. Specific examples are shown below.
  • Tertiary amine oxides or hydrates include N-methylmorpholine-N-oxide, N, N dimethylethanolamine-N oxide, N, N dimethylcyclohexylamine-N oxide, N, N, N Examples thereof include triethylamine-N oxide, N, N-dimethylbenzylamine N oxide, N-methylbiperidine N oxide, and the hydrates thereof.
  • N-methylmorpholine N-oxide monohydrate is preferred. These can be used alone or in combination of two or more.
  • Amides include formamide, ⁇ -methylformamide, ⁇ , ⁇ ⁇ ⁇ dimethylformamide, ⁇ , ⁇ jetylamide, acetoamide, ⁇ -methylacetamide, ⁇ , ⁇ dimethylacetamide, ⁇ -methyl-2-pyrrolidone, 1,3 dimethyl-2 And imidazolidinone.
  • ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylacetamide, ⁇ -methyl-2 pyrrolidone, 1,3 dimethyl-2-imidazolidinone are preferred. These can be used alone or in combination of two or more.
  • the metal halide include alkali metal halides and alkaline earth metal halides.
  • halogen-alkali metal examples include lithium bromide, lithium chloride, potassium chloride, potassium bromide or hydrates thereof.
  • halogen-alkali earth metal examples include salt calcium, magnesium chloride, Forces such as calcium bromide and magnesium bromide are preferably lithium halides or hydrates thereof, and lithium chloride (anhydrous) is particularly preferable. These can be used alone or in combination of two or more.
  • a preferred combination of amide and metal halide is N, N-dimethylacetamide, N-methyl-2 pyrrolidone, 1,3 dimethyl-2 imidazolidinone or a mixture thereof and lithium chloride.
  • the metal halide is preferably 3 to 15% by weight, more preferably 5 to 12%, based on the total of the amide and the metal halide.
  • the ionic liquid has a melting point of 150 ° C. or less, a room temperature (about 25 ° C.), a vapor pressure of zero (or substantially zero), a high melting power and a wide range! ⁇ With a liquid range! ⁇ It shall mean an organic compound salt having characteristics.
  • the ionic liquids can be used alone or in combination of two or more.
  • the cation M + is selected from an ammonium compound, an imidazolium compound, a pyridinium compound, or a phosphonium compound, and is selected as an ion or a halogen ion). I prefer something that is.
  • the ammonium compound as the cation M + of the ionic liquid includes, for example, an aliphatic quaternary ammonium compound, specifically, tetraptyl ammonium, tetrapentyl ammonium. And tetraalkylammonium compounds such as Similarly, imidazolium compounds as cation M + include, for example, 1-ethyl-3-methylimidazole, 1-butyl-3-methylimidazole, 1-hexylo 3-methylimidazolium, 1 decyl-3-methylimidazolium. And N, N, -dialkyl imidazolium compounds such as 1-butyl-2,3 dimethylimidazolium.
  • pyridinium compounds include N-alkylpyridium compounds such as 1-hexylpyridium, 1-butyl-3 methylpyridium, and 1-butyl-4 methylpyridium.
  • Examples of the phosphonium compound as cation M + include tetraalkylphosphonium compounds such as tetrabutylphosphonium, triisobutylmethylphosphonium, and trihexyltetradecylphosphonium.
  • anion X— which is a counter ion of these compounds, a chloro ion is preferable.
  • Examples of the polymer material that can be dissolved in the component (a) include cellulose, chitin, chitosan, animal fibers, and synthetic polymers.
  • cellulose In particular, from the viewpoint of effective utilization of natural resources, cellulose, chitin, chitosan and animal fibers are preferred, and cellulose is particularly preferred.
  • the cellulose is not particularly limited, and a known cellulose can be used. Specific examples of cellulose include cotton, wood-derived pulp, bacterial cellulose, algae, and sea squirt-derived cellulose. Cellulose having an average degree of polymerization of 10 to 20,000 can be used, and particularly preferably 150 to 5,000. In the case of using pulp, the shape of the pulp, which uses both dissolved pulp and paper pulp, includes sheet, powder, and flock.
  • the cellulose includes derivatized cellulose.
  • Cellulose derivatives include cellulose ethers, cellulose esters, cellulose strength rubamates, and the like. Specifically, methyl cellulose, ethyl cellulose, propyl cellulose, cellulose diacetate, cenorelose triacetate, hydroxypropyl cellulose, hydroxy.
  • Chitin is a natural polysaccharide in which N-acetyl-D-darcosamine is 1,4- ⁇ linked. Chitin is not particularly limited, and known ones can be used.
  • chitin derived from shrimp, crustacean crustaceans, insect exoskeletons such as power beetles, fungal cell walls, algae and the like can be used.
  • Chitin having an average degree of polymerization of 10 to 10,000 can be used, and preferably 100 to 8,000.
  • Chitosan is a basic polysaccharide in which chitin is deacetylated.
  • Chitosan is not particularly limited, and known ones can be used. Specifically, chitosan having a degree of deacetylation of up to 95% can be used, preferably 30 to 70%. Further, chitosan having an average degree of polymerization of 10 to: LO, 000 can be used, and preferably 100 to 8,000.
  • animal fibers include silk fiber mouth-in and wool, but are not limited thereto.
  • synthetic polymer various synthetic polymers such as polyethers, polyols, and polyesters can be used.
  • Polyvinyl alcohol, polyacrylo-tolyl, polybutyropyrrolidone, polychlorinated bulu, polybulu Examples include but are not limited to acetate.
  • the weight ratio of the component (1) and the component (2) in the polymer blend of the present invention can be appropriately changed according to the desired characteristics, application, and the like. From the point of change in properties due to blending, it is preferable that the weight ratio of component (1) to component (2) is 1:99 to 99: 1, more preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2.
  • the polymer blend of the present invention can generally be said to correspond to what is referred to as a compatible or miscible polymer blend, and comprises a (poly) polysaccharide containing (a) component, (1) component and (2) component. It can be prepared using a taxane-containing solution.
  • Examples of other components include an antioxidant. Specifically, gallic acid propylene, methyl gallate, ethyl gallate, gallic acid ester of isopropyl gallate; carbo-ro such as glyceraldehyde, L-ascorbic acid, isoscorbic acid, triose reductone, reductic acid, etc. Compound with adjacent double bond; ethylenediamine 4 Examples include acetic acid; inorganic salts such as calcium pyrophosphate, calcium chloride, and ammonium salt. In particular, propyl gallate is preferred.
  • additives such as a colorant, a plasticizer, a fragrance, a cross-linking agent, a surface treatment agent, and a pH adjusting agent may be mentioned.
  • a solvent other than the component (a) may be blended in the polymouth taxane-containing solution.
  • the component (a) is other than an amide or a halogenated metal, the amides mentioned in the component (a) may be preferably blended! / ⁇ .
  • a solvent may be blended that can be uniformly mixed with the component (a) and does not dissolve both the component (1) and the component (2).
  • Non-solvents include water; mixed solvents of water and lower alcohols (methanol, n-propanol, isopropanol, butanol); aprotic organic solvents such as toluene and xylene. Water is particularly preferable.
  • the polyortaxane-containing solution is prepared by mixing (1) component, (a) component, (2) component, and optionally other components, and stirring (1) component and (2) component. It can be prepared by dissolving. Alternatively, the solution of the component (a) to which the component (1) is added may be prepared separately from the solution of the component (a) to which the component (2) is added, and then these solutions may be mixed. In this case, the component (a) to which the component (1) is added and the component (a) to which the component (2) is added may be the same or different.
  • the dissolution temperature is not particularly limited and can be selected from the range in which component (a) exhibits fluidity. From the viewpoint of suppressing the decomposition of the components, the temperature is preferably in the range of room temperature to about 100 ° C, for example, in the range of room temperature to about 70 ° C.
  • the sum of the components (1) and (2) is 95% by weight or less in the solution, and the productivity is 0.5 to 50% by weight.
  • the polymer blend can be prepared by agglomerating the components (1) and (2) from a solution containing a polymouth taxane.
  • the agglomeration method is not particularly limited, and a known method can be used.
  • a polymouth taxane-containing solution is formed and brought into contact with a coagulation liquid to remove the component (a) and (1 ) And (2) components can be agglomerated.
  • the coagulation liquid include the non-solvents described above.
  • the coagulation solution can be obtained by adding a pH adjuster such as acetic acid.
  • Molded articles containing polymer blends can also be prepared by known methods.
  • a method in which a polymouth taxane-containing solution is discharged from a spinning nozzle into a coagulation bath, aggregated in a filament form, and taken out from the bath as a fiber can be employed.
  • the polymouth taxane-containing solution may be discharged from a spinning nozzle into the air, and the formed filamentous solution stream may be put into a coagulating liquid bath to be agglomerated.
  • a casting method in which a polymouth taxane-containing solution is cast and then brought into contact with a coagulation liquid in the next step V to agglomerate to form a film. It can also be prepared as a blown film by the inflation method.
  • Poly mouth taxane (PR) is as follows, and equivalent products can be purchased from Advanced Soft Materials Co., Ltd.
  • the linear molecule is PEG with an average molecular weight of 35,000. It has an adamantane group via an amide bond at the end.
  • the monocyclic molecule is ⁇ -CD, and the number of CDs included is 90-: LOO (inclusion rate is about 22-25%).
  • Cellulose is microcrystalline cellulose manufactured by Whatman and trade name CF11.
  • N, N dimethylacetamide (DMAc) is an experimental grade reagent manufactured by Wako Pure Chemical Industries, Ltd.
  • a molecular sieve 4A (manufactured by Wako Pure Chemical Industries, Ltd.) is placed in advance and left for a day. The water is removed.
  • Anhydrous lithium chloride (LiCl) is an experimental grade reagent manufactured by Wako Pure Chemical Industries, which has been dried at 105 ° C for 2 hours or more in advance.
  • Example 1 Preparation of molded article containing polymer blend
  • Methylmorpholine-4-oxide hydrate (NMMO) 9.5 g was melted by heating to 90 ° C, and crushed PR 250 mg and propyl gallate (PG) 5 mg were added. Heated for minutes. Next, add 250 mg of cellulose and stir at 100 ° C for an additional hour. A slightly viscous brown solution was obtained.
  • NMMO Methylmorpholine-4-oxide hydrate
  • the solution obtained above was deaerated by placing it in a vacuum dryer at 105 ° C. under vacuum for 10 to 15 minutes. 5 ml of the solution was cast in a Teflon petri dish ( ⁇ 50 mm) at a high temperature and further maintained at 105 ° C. for 10 minutes, and then cooled to room temperature in a desiccator and solidified. The solidified sample was immersed in a mixed solvent of methanol Z water (75Z25, v / v) to elute NMMO and PG. Washing with the mixed solvent was repeated twice, followed by washing with ion-exchanged water to obtain a white turbid gel-like molded product.
  • Example 2 Preparation of a film containing a polymer blend
  • NMM018g was melted by heating to 90 ° C., and PRlg and cellulose lg were added. When stirring with a magnetic stirrer, these dissolved and a translucent viscous solution was obtained, but some remained undissolved at the bottom of the container.
  • the solution obtained above is cast into a glass plate and then washed with methanol Z water (75 Z25, v / v) to elute NMMO and agglomerate the polymer blend of PR and cellulose. A slightly white translucent gel-like film was obtained.
  • Example 3 Preparation of fiber containing polymer blend
  • the solution (1) and the solution (2) were mixed at a volume ratio of 1: 2 to obtain a solution containing a poly (taxane) taxane.
  • the solution containing the polymouth taxane was extruded with a syringe into a beaker filled with methanol as a coagulation bath, and the polymer blend was coagulated into filaments and precipitated on the bottom surface. This was wound up on a centrifuge tube, heated at 60 ° C. and dried to obtain a fiber having a thickness of about 180 / zm.
  • the solution (1) and the solution (2) were mixed at a volume ratio of 1: 1, 2: 1, respectively, polypolytaxane-containing solutions were obtained and spun by the same method as described above. A 180 m fiber was obtained.
  • Example 4 Preparation of fiber containing polymer blend and evaluation of physical properties
  • the solution (1) and the solution (2) were mixed so that the weight ratio of the polymouth taxane to cellulose was the ratio shown in Table 1 below to obtain a polymouth taxane-containing solution. Then, using these solutions, fibers of Examples 4-1 to 4-3 were obtained in the same manner as in Example 3 (thickness: about 180 m).
  • a solution containing a poly (taxane) taxan was obtained in the same manner as in the solution (2) except that the amount of poly (taxane) added was 10 g. Then, using this solution, a fiber of Comparative Example 2 containing only a polymouth taxane was obtained (thickness of about 90) in the same manner as in Example 3 (extruding was performed using a nozzle having a small diameter). / ⁇ ⁇ ).
  • the present invention provides a new material that can be formed into fibers and films.
  • the present invention expands the possibilities as a raw material for poly-oral taxanes, and in recent years, the shape and physical properties of molded products using natural products such as cellulose, chitin, chitosan, etc., which are also attracting attention as a resource exhaustion problem. Application to can be expected.

Abstract

A polymer blend composed of polyrotaxane and other polymer material; and a molded item containing the same. There is provided a polymer blend comprising (1) polyrotaxane and (2)(a) polymer material soluble in at least one solvent, selected from the group consisting of a tertiary amine oxide or hydrate thereof; an amide and metal halide; and an ionic liquid. Further, there is provided a molded item containing the polymer blend.

Description

明 細 書  Specification
ポリ口タキサンのポリマーブレンド及びその使用  Polymer blends of polymouth taxanes and uses thereof
技術分野  Technical field
[0001] 本発明は、新規なポリ口タキサンのポリマーブレンド及びこのポリマーブレンドを含 む成形品に関する。  [0001] The present invention relates to a polymer blend of a novel polyortaxane and a molded article containing the polymer blend.
背景技術  Background art
[0002] ポリ口タキサンは、環状分子(回転子: rotator)の開口部が直鎖状分子 (軸: axis)に よって串刺し状に貫かれ、環状分子が直鎖状分子を包接してなる擬ポリロタキサンの 両末端 (直鎖状分子の両末端)に、環状分子が遊離しないようにブロック基を配置し てなる。代表的には、環状分子として α—シクロデキストリン (以下、シクロデキストリン を単に「CD」と略記する場合がある)、直鎖状分子としてポリエチレングリコール (以下 、「PEG」と略記する場合がある)を用いたポリ口タキサンが挙げられ (例えば、特許文 献 1参照)、これらについての応用が近年、盛んに行われている。  [0002] Polymouth taxanes are pseudo molecules in which the opening of a cyclic molecule (rotator) is pierced by a linear molecule (axis), and the cyclic molecule includes the linear molecule. Blocking groups are arranged at both ends of the polyrotaxane (both ends of the linear molecule) so that the cyclic molecule is not released. Typically, α-cyclodextrin as a cyclic molecule (hereinafter, cyclodextrin may be simply abbreviated as “CD”) and polyethylene glycol as a linear molecule (hereinafter sometimes abbreviated as “PEG”) (See, for example, Patent Document 1), and these have been actively applied in recent years.
[0003] 応用の一つとして着目されているの力 他の高分子材料とのブレンドである。すな わち他の高分子材料由来の特性を維持しつつ、新たな特性をポリ口タキサンにより導 入しょうというものである。ブレンドを製造する一つの方法力 ブレンドしょうとする材 料の共通溶媒を用いて、材料を混合し、均一な溶液を形成させることを利用する方 法である。しかしながら、ポリ口タキサンの場合、これまでに知られていた良溶媒は、 ジメチルスルホキシド(DMSO)又は NaOH水溶液のみであり、ブレンドを開発する 上での大きな障害となっていた (例えば、非特許文献 1〜3参照)。  [0003] The power that is attracting attention as one of the applications is a blend with other polymer materials. In other words, while maintaining the properties derived from other polymer materials, we will introduce new properties with a poly-oral taxane. One method of manufacturing blends This is a method that uses a common solvent of the materials to be blended to mix the materials to form a uniform solution. However, in the case of poly (oral taxanes), the only good solvents known so far are dimethyl sulfoxide (DMSO) or aqueous NaOH solution, which has been a major obstacle in developing blends (for example, non-patent literature). 1 to 3).
特許文献 1:特許第 2810264号公報  Patent Document 1: Japanese Patent No. 2810264
非特許文献 l : Harada, A.; Li, J.; Kamachi, M. Macromolecules 1990,23, 2821-2823 非特許文献 2 : Harada, A.; Li, J.; Kamachi, M. Nature 1992, 356,325-327 非特許文献 3 : Harada, A.; Li, J.; Kamachi, M. Nature 1993, 364, 516-518 発明の開示  Non-patent literature l: Harada, A .; Li, J .; Kamachi, M. Macromolecules 1990, 23, 2821-2823 Non-patent literature 2: Harada, A .; Li, J .; Kamachi, M. Nature 1992, 356,325 -327 Non-Patent Document 3: Harada, A .; Li, J .; Kamachi, M. Nature 1993, 364, 516-518 Disclosure of the Invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0004] 本発明の目的は、ポリ口タキサン及び他の高分子材料力 なるポリマーブレンドを 提供することであり、また、このポリマーブレンドを含む成形品を提供することである。 課題を解決するための手段 [0004] An object of the present invention is to provide a polymer blend that is a polymouth taxane and other polymer materials. It is to provide and to provide a molded article comprising this polymer blend. Means for solving the problem
[0005] 本発明者らは、第三級アミンォキシド又はその水和物、アミド及びハロゲンィ匕金属 並びにイオン性液体がポリ口タキサンの良溶媒であり、これに溶解しうる他の高分子 材料とポリ口タキサンのポリマーブレンドを形成することが可能であることを見出し、本 発明を完成するに至った。  [0005] The present inventors have found that tertiary amine oxides or their hydrates, amides and halogenated metals, and ionic liquids are good solvents for polyoral taxanes, and other polymeric materials and polymers that can be dissolved therein. We have found that it is possible to form a polymer blend of an oral taxane and have completed the present invention.
[0006] すなわち、本発明は、(1)ポリ口タキサン、並びに(2) (a)第三級アミンォキシド又は その水和物;アミド及びハロゲンィ匕金属;並びにイオン性液体力もなる群より選択され る溶媒の少なくとも 1種に溶解しうる高分子材料力もなるポリマーブレンドに関する。ま た、本発明は、このポリマーブレンドを含む繊維、フィルムといった成形品に関する。 発明の効果  [0006] That is, the present invention is selected from the group consisting of (1) a polyoral taxane, and (2) (a) a tertiary amine oxide or a hydrate thereof; an amide and a halogenated metal; and an ionic liquid force. The present invention relates to a polymer blend that also has a polymer material power that can be dissolved in at least one solvent. The present invention also relates to a molded article such as a fiber or film containing the polymer blend. The invention's effect
[0007] 本発明のポリ口タキサン及び他の高分子材料力 なるポリマーブレンドによれば、他 の高分子材料の物性を大きく変化させることなぐポリ口タキサン由来の特性 (強度、 弾性、吸水性又は伸び等)を新たに付与することが可能となり、利用価値が高い。特 にポリ口タキサンは架橋させることにより、上記の特性を著しく向上させることが知られ ており、これを利用して、これまでにない優れた物性を有する材料を得ることが可能 になる。本発明のポリ口タキサン及び他の高分子材料力 なるポリマーブレンドは、容 易に繊維、フィルム等の成形品とすることができ、有用性が高い。  [0007] According to the polymer blend of the present invention polypolytaxane and other polymer material strength, properties derived from the polymouthtaxane (strength, elasticity, water absorption or (E.g., growth) can be newly added, and the utility value is high. In particular, it is known that the above-mentioned properties can be remarkably improved by crosslinking the poly (taxane) taxane. By using this, it becomes possible to obtain a material having unprecedented physical properties. The polyblend taxane of the present invention and other polymer blends having high polymer materials can be easily formed into molded articles such as fibers and films, and are highly useful.
図面の簡単な説明  Brief Description of Drawings
[0008] [図 1]例 3の溶液(1)と溶液 (2)を体積比 1: 2で調製したポリ口タキサン含有溶液を用 V、た繊維の顕微鏡写真である。  [0008] FIG. 1 is a photomicrograph of fibers obtained using a solution containing a poly (taxane) taxane prepared from the solution (1) and the solution (2) of Example 3 at a volume ratio of 1: 2.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0009] (1)成分: [0009] (1) Component:
本発明において、ポリ口タキサンとは、環状分子の開口部が直鎖状分子によって串 刺し状に貫かれ、環状分子が直鎖状分子を包接してなる擬ポリロタキサンの両末端 ( 直鎖状分子の両末端)に、環状分子が遊離しないようにブロック基を配置した分子を いう。 [0010] 直鎖状分子は、環状分子に包接され、非共有結合的に一体化することができる分 子又は物質であって、直鎖状のものであれば、特に限定されず、高分子を含むいか なる分子を用いてもよい。 In the present invention, the polyortaxane refers to a quasi-polyrotaxane in which openings of a cyclic molecule are pierced by linear molecules and the cyclic molecules include the linear molecules (both linear molecules). A molecule in which blocking groups are arranged so that the cyclic molecule is not released at both ends. [0010] A linear molecule is a molecule or substance that is included in a cyclic molecule and can be integrated non-covalently, and is not particularly limited as long as it is linear. Any molecule, including molecules, may be used.
[0011] ここで、「直鎖状分子」の「直鎖」は、実質的に「直鎖」であることを意味する。即ち、 回転子である環状分子が回転可能、あるいは直鎖状分子上で環状分子が摺動又は 移動可能であれば、直鎖状分子は分岐鎖を有していてもよい。また、「直鎖」の長さ は、直鎖状分子上で環状分子が摺動又は移動可能であれば、その長さに特に制限 はない。  [0011] Here, "linear" of "linear molecule" means substantially "linear". That is, the linear molecule may have a branched chain as long as the cyclic molecule as a rotor is rotatable or the cyclic molecule is slidable or movable on the linear molecule. Further, the length of the “linear” is not particularly limited as long as the cyclic molecule can slide or move on the linear molecule.
[0012] また、「直鎖状分子」の「直鎖」は、ポリ口タキサン材料との関係で、相対的に決まる。  In addition, the “straight chain” of the “linear molecule” is relatively determined depending on the relationship with the polymouth taxane material.
即ち、架橋構造を一部に有する材料の場合、直鎖状分子は、材料中においてごく一 部である場合もあり得る。ごく一部であっても、上記のように、直鎖状分子上で環状分 子が摺動又は移動可能であれば、その長さに特に制限はない。  That is, in the case of a material having a crosslinked structure in part, the linear molecule may be only a part in the material. Even if it is only a small part, the length is not particularly limited as long as the cyclic molecule can slide or move on the linear molecule as described above.
[0013] 直鎖状分子としては、親水性ポリマー及び疎水性ポリマーのいずれも使用すること ができる。親水性ポリマーとしては、例えばポリビュルアルコールやポリビュルピロリド ン、ポリ(メタ)アクリル酸、セルロース系榭脂(カルボキシメチルセルロース、ヒドロキシ ェチルセルロース、ヒドロキシプロピルセルロース等)、ポリアクリルアミド、ポリエチレ ンォキシド、ポリエチレングリコール、ポリビュルァセタール系榭脂、ポリビュルメチル エーテル、ポリアミン、ポリエチレンィミン、カゼイン、ゼラチン、でんぷん等及び Z又 はこれらの共重合体等が挙げることができ;疎水性ポリマーとしては、例えばポリェチ レン、ポリプロピレン、及びその他ォレフィン系単量体との共重合榭脂等のポリオレフ イン系榭脂、ポリエステル榭脂、ポリ塩化ビュル榭脂、ポリスチレンやアクリロニトリル —スチレン共重合榭脂等のポリスチレン系榭脂、ポリメチルメタタリレートや (メタ)アタリ ル酸エステル共重合体、アクリロニトリル メチルアタリレート共重合榭脂等のアクリル 系榭脂、ポリカーボネート榭脂、ポリウレタン榭脂、塩ィ匕ビュル 酢酸ビニル共重合 榭脂、ポリビニルブチラール榭脂等;並びにこれらの誘導体又は変性体を挙げること ができる。この他に、ポリイソブチレン、ポリテトラヒドロフラン、ポリア二リン、アタリロニト リル ブタジエン スチレン共重合体 (ABS榭脂)、ナイロンなどのポリアミド類、ポリ イミド類、ポリイソプレン、ポリブタジエンなどのポリジェン類、ポリジメチルシロキサン などのポリシロキサン類、ポリスルホン類、ポリイミン類、ポリ無水酢酸類、ポリ尿素類、 ポリスルフイド類、ポリフォスファゼン類、ポリケトン類、ポリフヱ-レン類、ポリハロォレ フィン類、並びにこれらの誘導体なども使用することができる。 [0013] As the linear molecule, both a hydrophilic polymer and a hydrophobic polymer can be used. Examples of the hydrophilic polymer include polybutanol, polypyrrole pyrrolidone, poly (meth) acrylic acid, cellulose-based resin (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc.), polyacrylamide, polyethyleneoxide, polyethylene. Examples include glycols, polybulacetal resin, polybulumethyl ether, polyamines, polyethyleneimine, casein, gelatin, starch, and Z or copolymers thereof; examples of hydrophobic polymers include Polyolefin, polypropylene, and other polyolefin resins such as copolymer resins, polyester resins, polychlorinated butadiene resins, polystyrene and acrylonitrile-styrene copolymers such as styrene copolymer resins Acrylic resins such as tyrene-based resin, polymethylmetatalylate, (meth) acrylate copolymer, acrylonitrile methyl acrylate copolymer resin, polycarbonate resin, polyurethane resin, salt resin Examples thereof include vinyl copolymer resin, polyvinyl butyral resin, etc .; and derivatives or modified products thereof. Other than these, polyisobutylene, polytetrahydrofuran, polyarine, acrylonitrile butadiene styrene copolymer (ABS resin), polyamides such as nylon, polyimides such as polyimides, polyisoprene and polybutadiene, polydimethylsiloxane Polysiloxanes such as polysulfones, polysulfines, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and derivatives thereof should also be used Can do.
[0014] これらのうち、ポリエチレングリコール、ポリイソプレン、ポリイソブチレン、ポリブタジ ェン、ポリプロピレングリコール、ポリテトラヒドロフラン、ポリジメチルシロキサン、ポリエ チレン、及びポリプロピレンが好ましい。特にポリエチレングリコールであるのが好まし い。  Of these, polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene are preferable. Particularly preferred is polyethylene glycol.
[0015] 直鎖状分子は、数平均分子量が 1, 000以上、例えば 1, 000-1, 000, 000であ ること力 子まし ヽ。より好ましくは 5, 000以上、 ί列えば、 5, 000〜1, 000, 000又は 5, 000〜500, 000、さらに好まし <は 10, 000以上、例えば 10, 000〜1, 000, 000 、 10, 000〜500, 000又は 10, 000〜300, 000である。  [0015] The linear molecule should have a number average molecular weight of 1,000 or more, for example, 1,000-1, 000, 000. More preferably, 5,000 or more, 5,000 to 1,000,000 or 5,000 to 500,000, even more preferable <is 10,000 or more, for example, 10,000 to 1,000,000 10,000 to 500,000 or 10,000 to 300,000.
[0016] 直鎖状分子は、その両末端に反応基を有するのが好ましい。反応基を有することに より、ブロック基と容易に反応することができる。反応基は、用いるブロック基に依存す る力 例えば水酸基、アミノ基、カルボキシル基、チオール基等を挙げることができる  [0016] The linear molecule preferably has reactive groups at both ends. By having a reactive group, it can easily react with a blocking group. Examples of reactive groups include forces that depend on the block group used, such as hydroxyl groups, amino groups, carboxyl groups, and thiol groups.
[0017] 環状分子としては、種々のシクロデキストリン類、例えば α—シクロデキストリン、 β —シクロデキストリン又は Ί—シクロデキストリン等の未修飾のシクロデキストリン類を 挙げることができる。一般に環状分子がシクロデキストリン類であるポリ口タキサンは、 特に不溶性で良溶媒が少ないことが知られている。この不溶性は、シクロデキストリン 上に存在する水酸基が、分子内 Ζ分子間水素結合を形成するためと考えられている ものの、詳細なメカニズムは不明である。これらのシクロデキストリン類は、ジメチルシ クロデキストリン、ヒドロキシプロビルシクロデキストリン、ヒドロキシェチルシクロデキスト リン、ァセチルシクロデキストリン等、その水酸基が部分的に修飾されたものであって ちょい。 [0017] Examples of the cyclic molecule include various cyclodextrins, for example, unmodified cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and Ί -cyclodextrin. In general, it is known that a polyoral taxane whose cyclic molecule is a cyclodextrin is particularly insoluble and has few good solvents. This insolubility is thought to be because the hydroxyl groups present on the cyclodextrin form intramolecular and intermolecular hydrogen bonds, but the detailed mechanism is unknown. These cyclodextrins are dimethyl cyclodextrins, hydroxypropyl cyclodextrins, hydroxyethyl cyclodextrin, acetyl cycloalkyl cyclodextrins, etc., which have partially modified hydroxyl groups.
[0018] 上述のシクロデキストリン類は、その種類により環状分子の開口部の大きさが異なる 。したがって、用いる直鎖状分子の種類、具体的には用いる直鎖状分子を円柱状と 見立てた場合、その円柱の断面の直径、直鎖状分子の疎水性又は親水性等により、 用いる環状分子を選択することができる。また、開口部が相対的に大きな環状分子と 、相対的に直径が小さな円柱状の直鎖状分子を用いた場合、環状分子の開口部に[0018] The above cyclodextrins have different sizes of the opening of the cyclic molecule depending on the type. Therefore, the type of linear molecule to be used, specifically, when the linear molecule to be used is assumed to be cylindrical, the cyclic molecule to be used depends on the diameter of the cross section of the cylinder, the hydrophobicity or hydrophilicity of the linear molecule, etc. Can be selected. Also, cyclic molecules with relatively large openings When using a cylindrical linear molecule with a relatively small diameter,
2以上の直鎖状分子を包接することもできる。 Two or more linear molecules can be included.
[0019] ブロック基は、環状分子が直鎖状分子により串刺し状になった形態を保持する基で あれば、特に限定されず、いかなる基を用いてもよい。このような基として、例えば「嵩 高さ」を有する基及び Z又は「イオン性」を有する基等を挙げることができる。ここで、「 基」というのは、分子基及び高分子基を含めた種々の基を意味する。即ち、「嵩高さ」 を有する基として、模式的に、球形で表される基であっても、側壁のように表される固 体支持体であってもよい。また、「イオン性」を有する基の「イオン性」と、環状分子の 有する「イオン性」とが影響しあうことにより、例えば反発しあうことにより、環状分子が 直鎖状分子により串刺し状になった形態を保持することができる。 [0019] The blocking group is not particularly limited as long as it is a group that retains a form in which a cyclic molecule is skewered by a linear molecule, and any group may be used. Examples of such a group include a group having “bulkiness” and a group having Z or “ionicity”. Here, the “group” means various groups including a molecular group and a polymer group. That is, the group having “bulkyness” may be a group that is schematically represented by a sphere or a solid support represented by a side wall. In addition, the “ionicity” of the group having “ionicity” and the “ionicity” of the cyclic molecule influence each other, for example, by repulsion, the cyclic molecule is skewered by a linear molecule. It is possible to retain the form.
[0020] また、ブロック基は、上述のように、串刺し状になった形態を保持するものであれば 、高分子の主鎖であっても側鎖であってもよい。ブロック基が高分子 Aである場合、マ トリタスとして高分子 Aがあり、その一部に架橋構造が含まれる形態であっても、逆に マトリクスとして架橋構造を含むポリ口タキサン材料があり、その一部に高分子 Aが含 まれる形態であってもよい。このように、種々の特性を有する高分子 Aと組み合せるこ とにより、ポリ口タキサン材料の特性と高分子 Aの特性とを組み合せて有する複合材 料を形成することができる。  [0020] Further, the blocking group may be a polymer main chain or a side chain as long as it retains a skewered shape as described above. When the blocking group is polymer A, there is polymer A as matrix, and there is a polymouth taxane material containing a crosslinked structure as a matrix, even if part of it contains a crosslinked structure. A form in which polymer A is partially contained may be used. As described above, by combining with the polymer A having various properties, a composite material having a combination of the properties of the polymouth taxane material and the properties of the polymer A can be formed.
[0021] ブロック基としては、 2, 4—ジニトロフエ-ル基、 3, 5—ジニトロフエ-ル基等のジ- トロフエニル基類、シクロデキストリン類、ァダマンタン基類、トリチル基類、フルォレセ イン類及びピレン類、並びにこれらの誘導体又は変性体を挙げることができる。より具 体的には、環状分子として α—シクロデキストリン、及び直鎖状分子としてポリェチレ ングリコールを用いる場合であっても、ブロック基としてシクロデキストリン類、 2, 4— ジ-トロフエ-ル基、 3, 5—ジ-トロフエ-ル基等のジ-トロフエ-ル基類、ァダマンタ ン基類、トリチル基類、フルォレセイン類及びピレン類、並びにこれらの誘導体又は 変性体を挙げることができる。  [0021] Examples of the blocking group include 2,4-dinitrophenyl group, 3,5-dinitrophenyl group and other di-trophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, and pyrene. And derivatives or modified products thereof. More specifically, even when α-cyclodextrin is used as a cyclic molecule and polyethylene glycol is used as a linear molecule, cyclodextrin, 2, 4-di-trifluoro group as a blocking group, Examples thereof include di-trifluoro groups such as 3,5-di-phenol groups, adamantane groups, trityl groups, fluoresceins and pyrenes, and derivatives or modified products thereof.
[0022] 擬ポリロタキサンの調製の際、直鎖状分子で串刺し状に貫かれる環状分子の量を 制御するのが好ましい。少なくとも 2個の環状分子を直鎖状分子で串刺し状に貫き、 少なくとも 2個の環状分子が直鎖状分子を包接してなるのが好ましい。また、環状分 子が直鎖状分子上に最大限に存在することができる量、即ち最大包接量を 1とした 場合、環状分子の量は、最大包接量の 0. 001-0. 6、好ましくは 0. 01〜0. 5、より 好ましくは 0. 05-0. 4の値で存在するのが好ましい。 [0022] During the preparation of the pseudopolyrotaxane, it is preferable to control the amount of the cyclic molecule penetrating in a straight chain molecule. It is preferable that at least two cyclic molecules are pierced with linear molecules, and at least two cyclic molecules include the linear molecules. In addition, the ring segment When the maximum amount of a molecule can be present on a linear molecule, that is, when the maximum inclusion amount is 1, the amount of cyclic molecules is 0.001 to 0.6, preferably the maximum inclusion amount. It is preferably present at a value of 0.01 to 0.5, more preferably 0.05 to 0.4.
[0023] ポリ口タキサンは、好ましくはシクロデキストリン類、特に (X—シクロデキストリンカ、ポ リエチレングリコールを包接する擬ポリロタキサンにブロック基 (ァダマンタン基、ジ-ト 口フエ-ル基等)を配置したポリ口タキサンである。 [0023] Preferably, polypolytaxanes have cyclodextrins, in particular (X-cyclodextrinca, pseudopolyrotaxane clathrating polyethylene glycol with blocking groups (adamantane groups, ditophole groups, etc.). Polymouth taxane.
[0024] (2)成分: [0024] Component (2):
(2)成分は、 (a)第三級アミンォキシド又はその水和物;アミド及びハロゲンィ匕金属; 並びにイオン性液体力 なる群より選択される溶媒の少なくとも 1種に溶解しうる高分 子材料である。高分子材料は、(1)成分を含まないこととする。  The component (2) is a polymer material that can be dissolved in at least one solvent selected from the group consisting of (a) tertiary amine oxides or hydrates thereof; amides and halogenated metals; and ionic liquid forces. is there. The polymer material does not contain the component (1).
[0025] なお、(a)成分は、(1)成分をも溶解しうる溶媒であり、(1)及び (2)成分の共通溶 媒として機能しうるものである。(a)成分は、常温では固体であるが、加熱、好ましくは 40〜150°Cの加熱により流動性を示し、溶媒として機能しうるものも含むこととする。 具体例を以下に示す。  [0025] The component (a) is a solvent that can also dissolve the component (1), and can function as a common solvent for the components (1) and (2). The component (a) is a solid at room temperature, but includes those that exhibit fluidity by heating, preferably 40 to 150 ° C., and can function as a solvent. Specific examples are shown below.
[0026] 第三級アミンォキシド又はその水和物:  [0026] Tertiary amine oxide or hydrate thereof:
第三級アミンォキシド又はその水和物としては、 N—メチルモルホリン— N—ォキシ ド、 N, N ジメチルエタノールァミン— N ォキシド、 N, N ジメチルシクロへキシ ルァミン—N ォキシド、 N, N, N トリエチルァミン—N ォキシド、 N, N ジメチ ルベンジルァミン N ォキシド、 N メチルビペリジン N ォキシド等及びそれら の水和物が挙げられる。特に、 N メチルモルホリン N ォキシド · 1水和物が好ま しい。これらは、単独で、または 2種以上を組み合せて使用することができる。  Tertiary amine oxides or hydrates include N-methylmorpholine-N-oxide, N, N dimethylethanolamine-N oxide, N, N dimethylcyclohexylamine-N oxide, N, N, N Examples thereof include triethylamine-N oxide, N, N-dimethylbenzylamine N oxide, N-methylbiperidine N oxide, and the hydrates thereof. In particular, N-methylmorpholine N-oxide monohydrate is preferred. These can be used alone or in combination of two or more.
[0027] アミド及びハロゲンィ匕金属:  [0027] Amides and halogenated metals:
アミドとしては、ホルムアミド、 Ν—メチルホルムアミド、 Ν, Ν ジメチルホルムアミド 、 Ν, Ν ジェチルホルムアミド、ァセトアミド、 Ν—メチルァセトアミド、 Ν, Ν ジメチ ルァセトアミド、 Ν—メチルー 2 ピロリドン、 1, 3 ジメチルー 2 イミダゾリジノン等 が挙げられる。特に、 Ν, Ν ジメチルァセトアミド、 Ν—メチル—2 ピロリドン、 1, 3 ジメチルー 2—イミダゾリジノンが好ましい。これらは、単独で、または 2種以上を組 み合せて使用することができる。 [0028] また、ハロゲン化金属としては、ハロゲン化アルカリ金属又はハロゲン化アルカリ土 類金属が挙げられる。ハロゲンィ匕アルカリ金属としては、臭化リチウム、塩化リチウム、 塩ィ匕カリウム、臭化カリウム又はそれらの水和物等が挙げられ、ハロゲンィ匕アルカリ土 類金属としては、塩ィ匕カルシウム、塩化マグネシウム、臭化カルシウム、臭化マグネシ ゥム等が挙げられる力 好ましくはハロゲン化リチウム又はその水和物であり、特に塩 ィ匕リチウム (無水)が好ましい。これらは、単独で、または 2種以上を組み合せて使用 することができる。 Amides include formamide, Ν-methylformamide, Ν, ジ メ チ ル dimethylformamide, Ν, Ν jetylamide, acetoamide, Ν-methylacetamide, Ν, Ν dimethylacetamide, Ν-methyl-2-pyrrolidone, 1,3 dimethyl-2 And imidazolidinone. In particular, Ν, ジ メ チ ル dimethylacetamide, Ν-methyl-2 pyrrolidone, 1,3 dimethyl-2-imidazolidinone are preferred. These can be used alone or in combination of two or more. [0028] Examples of the metal halide include alkali metal halides and alkaline earth metal halides. Examples of the halogen-alkali metal include lithium bromide, lithium chloride, potassium chloride, potassium bromide or hydrates thereof. Examples of the halogen-alkali earth metal include salt calcium, magnesium chloride, Forces such as calcium bromide and magnesium bromide are preferably lithium halides or hydrates thereof, and lithium chloride (anhydrous) is particularly preferable. These can be used alone or in combination of two or more.
[0029] 好ましいアミドとハロゲン化金属の組み合わせは、 N, N—ジメチルァセトアミド、 N ーメチルー 2 ピロリドン、 1, 3 ジメチルー 2 イミダゾリジノン又はこれらの混合物 と、塩化リチウムである。  [0029] A preferred combination of amide and metal halide is N, N-dimethylacetamide, N-methyl-2 pyrrolidone, 1,3 dimethyl-2 imidazolidinone or a mixture thereof and lithium chloride.
[0030] ハロゲン化金属は、アミドとハロゲン化金属の合計中、 3〜 15重量%であることが好 ましぐより好ましくは 5〜 12%である。  [0030] The metal halide is preferably 3 to 15% by weight, more preferably 5 to 12%, based on the total of the amide and the metal halide.
[0031] イオン性液体:  [0031] Ionic liquid:
本発明において、イオン性液体は、融点が 150°C以下、室温 (約 25°C)で蒸気圧が ゼロ(又は実質的にゼロ)であって、高 ヽ溶解力と広!ヽ液体範囲を有すると!ヽぅ特徴 を有する有機化合物塩を意味するものとする。イオン性液体は、単独で、または 2種 以上を組み合せて使用することができる。  In the present invention, the ionic liquid has a melting point of 150 ° C. or less, a room temperature (about 25 ° C.), a vapor pressure of zero (or substantially zero), a high melting power and a wide range!と With a liquid range!有機 It shall mean an organic compound salt having characteristics. The ionic liquids can be used alone or in combination of two or more.
[0032] イオン性液体としては、式: M+X—  [0032] As the ionic liquid, the formula: M + X—
(式中、カチオン M+は、アンモ-ゥム化合物、イミダゾリゥム化合物、ピリジ-ゥムィ匕 合物又はホスホ-ゥム化合物力 選択され、ァ-オン ΧΊま、ハロゲンァ-オン力 選 択される)で示されるものが好ま 、。  (In the formula, the cation M + is selected from an ammonium compound, an imidazolium compound, a pyridinium compound, or a phosphonium compound, and is selected as an ion or a halogen ion). I prefer something that is.
[0033] イオン性液体のカチオン M+としてのアンモ-ゥム化合物には、例えば、脂肪族四 級アンモ-ゥム化合物、具体的には、テトラプチルアンモ-ゥム、テトラペンチルアン モ -ゥムのようなテトラアルキルアンモ-ゥム化合物が挙げられる。同様に、カチオン M+としてのイミダゾリゥム化合物には、例えば、 1ーェチルー 3—メチルイミダゾリゥム 、 1ーブチルー 3—メチルイミダゾリゥム、 1一へキシルー 3—メチルイミダゾリゥム、 1 デシルー 3—メチルイミダゾリゥム、 1ーブチルー 2, 3 ジメチルイミダゾリゥムのような N, N,—ジアルキルイミダゾリゥム化合物が挙げられる。更に、カチオン M+としての ピリジ -ゥム化合物には、 1一へキシルピリジ-ゥム、 1ーブチルー 3 メチルピリジ- ゥム、 1ーブチルー 4 メチルピリジ-ゥムのような N—アルキルピリジ-ゥム化合物が 挙げられる。また、カチオン M+としてのホスホ-ゥム化合物には、テトラブチルホスホ ユウム、トリイソブチルメチルホスホ-ゥム、トリへキシルテトラデシルホスホ -ゥムのよう なテトラアルキルホスホ-ゥム化合物が挙げられる。これらの化合物の対イオンである ァニオン X—としては、クロロイオンが好ましい。 [0033] The ammonium compound as the cation M + of the ionic liquid includes, for example, an aliphatic quaternary ammonium compound, specifically, tetraptyl ammonium, tetrapentyl ammonium. And tetraalkylammonium compounds such as Similarly, imidazolium compounds as cation M + include, for example, 1-ethyl-3-methylimidazole, 1-butyl-3-methylimidazole, 1-hexylo 3-methylimidazolium, 1 decyl-3-methylimidazolium. And N, N, -dialkyl imidazolium compounds such as 1-butyl-2,3 dimethylimidazolium. Furthermore, as cation M + Examples of pyridinium compounds include N-alkylpyridium compounds such as 1-hexylpyridium, 1-butyl-3 methylpyridium, and 1-butyl-4 methylpyridium. Examples of the phosphonium compound as cation M + include tetraalkylphosphonium compounds such as tetrabutylphosphonium, triisobutylmethylphosphonium, and trihexyltetradecylphosphonium. As anion X— which is a counter ion of these compounds, a chloro ion is preferable.
[0034] 特に、 1ーェチルー 3—メチルイミダゾリゥムクロリド、 1ーブチルー 3—メチルイミダゾ リウムクロリド、 1—へキシル 3—メチルイミダゾリゥムクロリド、 1—デシルー 3—メチ ルイミダゾリゥムクロリドのような N, N,ージアルキルイミダゾリゥムのハロゲン化物、とり わけ塩化物、又は 1一へキシルピリジ-ゥムクロリドのような N—アルキルピリジ-ゥム のハロゲン化物、とりわけ塩化物が好ましい。  [0034] In particular, such as 1-ethyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-hexyl 3-methylimidazolium chloride, 1-decyl-3-methyimidazolium chloride N, N, -dialkylimidazolium halides, in particular chlorides, or N-alkylpyridium chlorides such as 1-hexylpyridium chloride, in particular chlorides, are preferred.
[0035] (a)成分に溶解しうる高分子材料としては、例えば、セルロース、キチン、キトサン、 動物繊維、合成ポリマー等が挙げられる。  [0035] Examples of the polymer material that can be dissolved in the component (a) include cellulose, chitin, chitosan, animal fibers, and synthetic polymers.
[0036] 特に、天然資源の有効活用の点からは、セルロース、キチン、キトサン、動物繊維 が好ましぐとりわけセルロースが好ましい。  In particular, from the viewpoint of effective utilization of natural resources, cellulose, chitin, chitosan and animal fibers are preferred, and cellulose is particularly preferred.
[0037] セルロースは、特に制限されず、公知のものを用いることができる。具体的には、セ ルロースは、木綿、木材由来のパルプ、バクテリアセルロース、藻類、ホヤ由来のセ ルロース等を挙げることができる。また、セルロースは、平均重合度 10〜20, 000の ものを使用することができ、特に好ましくは 150〜5, 000である。パルプを使用する 場合は、溶解パルプ及び製紙用パルプのいずれもよぐパルプの形状としては、シー ト状、粉末状、フロック状等が挙げられる。  [0037] The cellulose is not particularly limited, and a known cellulose can be used. Specific examples of cellulose include cotton, wood-derived pulp, bacterial cellulose, algae, and sea squirt-derived cellulose. Cellulose having an average degree of polymerization of 10 to 20,000 can be used, and particularly preferably 150 to 5,000. In the case of using pulp, the shape of the pulp, which uses both dissolved pulp and paper pulp, includes sheet, powder, and flock.
[0038] なお、セルロースには、誘導体化されたセルロースも包含する。セルロース誘導体と しては、セルロースエーテル、セルロースエステル、セルロース力ルバメート類等が挙 げられ、具体的にはメチルセルロース、ェチルセルロース、プロピルセルロース、セル ロースジアセテート、セノレローストリアセテート、ヒドロキシプロピルセルロース、ヒドロキ シプロピノレメチノレセノレロース、トリチノレセノレロース、セノレロースフエ二ノレカノレノ メート、 カノレボキシメチノレセノレロース、スノレホェチノレセノレロース、ジェチノレアミノエチノレセノレ口 ース、第四級アンモ-ゥム塩を導入したセルロース等が挙げられる。 [0039] キチンは、 N—ァセチル— D—ダルコサミンが 1, 4— β結合している天然多糖類で ある。キチンは、特に制限されず、公知のものを使用することができる。具体的には、 キチンは、ェビ、力-等の甲殻類、力ブトムシ等の昆虫類の外骨格、菌類の細胞壁、 藻類等に由来するキチンを使用することができる。また、キチンは、平均重合度 10〜 10, 000のものを使用することができ、好ましくは 100〜8, 000である。 [0038] The cellulose includes derivatized cellulose. Cellulose derivatives include cellulose ethers, cellulose esters, cellulose strength rubamates, and the like. Specifically, methyl cellulose, ethyl cellulose, propyl cellulose, cellulose diacetate, cenorelose triacetate, hydroxypropyl cellulose, hydroxy. Cypropino Metino Resenorelose, Tritino Resenorelose, Senorelose Fuenorecanoleno Mate, Canoleboxy Methyleno Resenorelose, Snore Fetino Resenorelose, Jetinoreamino Ethino Resenore Mouth, Quaternary Ammonia Examples thereof include cellulose into which a salt is introduced. [0039] Chitin is a natural polysaccharide in which N-acetyl-D-darcosamine is 1,4-β linked. Chitin is not particularly limited, and known ones can be used. Specifically, chitin derived from shrimp, crustacean crustaceans, insect exoskeletons such as power beetles, fungal cell walls, algae and the like can be used. Chitin having an average degree of polymerization of 10 to 10,000 can be used, and preferably 100 to 8,000.
[0040] キトサンは、キチンを脱ァセチルイ匕した塩基性多糖である。キトサンは、特に制限さ れず、公知のものを使用することができる。具体的には、キトサンは、脱ァセチル化度 力 〜 95%のものを使用することができ、好ましくは 30〜70%である。また、キトサン は、平均重合度 10〜: LO, 000のものを使用することができ、好ましくは 100〜8, 00 0である。  [0040] Chitosan is a basic polysaccharide in which chitin is deacetylated. Chitosan is not particularly limited, and known ones can be used. Specifically, chitosan having a degree of deacetylation of up to 95% can be used, preferably 30 to 70%. Further, chitosan having an average degree of polymerization of 10 to: LO, 000 can be used, and preferably 100 to 8,000.
[0041] 動物繊維としては、絹フイブ口イン、羊毛等が挙げられるが、これらに制限されない  [0041] Examples of animal fibers include silk fiber mouth-in and wool, but are not limited thereto.
[0042] 合成ポリマーとしては、ポリエーテル類、ポリオール類、ポリエステル類をはじめとす る各種合成ポリマーが使用することができ、ポリビニルアルコール、ポリアクリロ-トリ ル、ポリビュルピロリドン、ポリ塩化ビュル、ポリビュルアセテート等が挙げられるがこ れらに限定されない。 [0042] As the synthetic polymer, various synthetic polymers such as polyethers, polyols, and polyesters can be used. Polyvinyl alcohol, polyacrylo-tolyl, polybutyropyrrolidone, polychlorinated bulu, polybulu Examples include but are not limited to acetate.
[0043] 本発明のポリマーブレンドにおける、(1)成分と(2)成分の重量割合は、所望の特 性、用途等に応じて、適宜、変動させることができる。ブレンドとすることによる特性の 変化の点からは、(1)成分と(2)成分の重量比が1 : 99〜99 : 1でぁることが好ましぐ より好ましくは 1: 9〜9: 1、さらに好ましくは 2: 8〜8: 2である。  [0043] The weight ratio of the component (1) and the component (2) in the polymer blend of the present invention can be appropriately changed according to the desired characteristics, application, and the like. From the point of change in properties due to blending, it is preferable that the weight ratio of component (1) to component (2) is 1:99 to 99: 1, more preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2.
[0044] 本発明のポリマーブレンドは、一般に、相溶性又は混和性のポリマーブレンドとい われるものに相当するということができ、(a)成分、(1)成分及び(2)成分を含む、ポリ 口タキサン含有溶液を用いて調製することができる。  [0044] The polymer blend of the present invention can generally be said to correspond to what is referred to as a compatible or miscible polymer blend, and comprises a (poly) polysaccharide containing (a) component, (1) component and (2) component. It can be prepared using a taxane-containing solution.
[0045] ポリ口タキサン含有溶液には、必要に応じて、他の成分を配合してもよ 、。  [0045] If necessary, other components may be blended into the polymouth taxane-containing solution.
[0046] 他の成分としては、例えば酸化防止剤が挙げられる。具体的には、没食子酸プロピ ル、没食子酸メチル、没食子酸ェチル、没食子酸イソプロピルの没食子酸エステル; グリセリンアルデヒド、 L—ァスコルビン酸、イソァスコルビン酸、トリオースレクダクトン 、レダクチン酸等のカルボ-ルー 2重結合が隣接している化合物;エチレンジァミン四 酢酸;ピロリン酸カルシウム、塩ィ匕カルシウム、塩ィ匕アンモ-ゥム等の無機塩が挙げら れる。特に没食子酸プロピルが好ましい。 [0046] Examples of other components include an antioxidant. Specifically, gallic acid propylene, methyl gallate, ethyl gallate, gallic acid ester of isopropyl gallate; carbo-ro such as glyceraldehyde, L-ascorbic acid, isoscorbic acid, triose reductone, reductic acid, etc. Compound with adjacent double bond; ethylenediamine 4 Examples include acetic acid; inorganic salts such as calcium pyrophosphate, calcium chloride, and ammonium salt. In particular, propyl gallate is preferred.
[0047] また、着色剤、可塑剤、香料、架橋剤、表面処理剤、 pH調製剤等の慣用の添加剤 ち挙げられる。  [0047] Further, conventional additives such as a colorant, a plasticizer, a fragrance, a cross-linking agent, a surface treatment agent, and a pH adjusting agent may be mentioned.
[0048] さらに、ポリ口タキサン含有溶液には、(a)成分以外の溶媒を配合してもよい。また( a)成分が、アミド及びハロゲンィ匕金属以外である場合は、好ましくは (a)成分で挙げ られたアミドを配合してもよ!/ヽ。  [0048] Furthermore, a solvent other than the component (a) may be blended in the polymouth taxane-containing solution. In addition, when the component (a) is other than an amide or a halogenated metal, the amides mentioned in the component (a) may be preferably blended! / ヽ.
[0049] また、(a)成分と均一に混合可能であり、(1)成分及び (2)成分をいずれも溶解しな い、溶媒 (非溶媒)を配合してもよい。非溶媒としては、水;水と低級アルコール (メタノ ール、 n—プロパノール、イソプロパノール、ブタノール)の混合溶媒;非プロトン系有 機溶剤、例えば、トルエン、キシレン等が挙げられる。特に水が好ましい。  [0049] Further, a solvent (non-solvent) may be blended that can be uniformly mixed with the component (a) and does not dissolve both the component (1) and the component (2). Non-solvents include water; mixed solvents of water and lower alcohols (methanol, n-propanol, isopropanol, butanol); aprotic organic solvents such as toluene and xylene. Water is particularly preferable.
[0050] ポリ口タキサン含有溶液は、(1)成分、(a)成分及び (2)成分、並びに場合によりそ の他の成分を混合'撹拌して、(1)成分及び (2)成分を溶解させることにより調製する ことができる。また、(1)成分を添加した (a)成分の溶液と、(2)成分を添加した (a)成 分の溶液とを別々に調製し、その後、これらの溶液を混合してもよい。この場合、 (1) 成分を添加する(a)成分と、(2)成分を添加する(a)成分は同一であっても、異なつ ていてもよい。溶解温度は、特に限定されず、(a)成分が流動性を示す範囲から選択 することができる。成分の分解を抑制する点からは室温〜 100°C程度の範囲であるこ と力 子ましく、例えば室温〜 70°C程度の範囲とすることができる。  [0050] The polyortaxane-containing solution is prepared by mixing (1) component, (a) component, (2) component, and optionally other components, and stirring (1) component and (2) component. It can be prepared by dissolving. Alternatively, the solution of the component (a) to which the component (1) is added may be prepared separately from the solution of the component (a) to which the component (2) is added, and then these solutions may be mixed. In this case, the component (a) to which the component (1) is added and the component (a) to which the component (2) is added may be the same or different. The dissolution temperature is not particularly limited and can be selected from the range in which component (a) exhibits fluidity. From the viewpoint of suppressing the decomposition of the components, the temperature is preferably in the range of room temperature to about 100 ° C, for example, in the range of room temperature to about 70 ° C.
[0051] 例えば、(1)及び(2)成分の合計は、溶液中、 95重量%以下であり、生産性の点 力らは 0. 5〜50重量%である。  [0051] For example, the sum of the components (1) and (2) is 95% by weight or less in the solution, and the productivity is 0.5 to 50% by weight.
[0052] ポリマーブレンドは、ポリ口タキサン含有溶液から、(1)及び(2)成分を凝集させるこ とにより調製することができる。凝集方法は、特に限定されず、公知の方法を用いるこ とができ、例えば、ポリ口タキサン含有溶液を成形し、これを凝固液に接触させて、 (a )成分を除去するとともに、(1)及び (2)成分を凝集させることができる。凝固液として は、上述の非溶媒が挙げられる。なお、凝固液には、酢酸等の pH調整剤を添加する ことちでさる。  [0052] The polymer blend can be prepared by agglomerating the components (1) and (2) from a solution containing a polymouth taxane. The agglomeration method is not particularly limited, and a known method can be used. For example, a polymouth taxane-containing solution is formed and brought into contact with a coagulation liquid to remove the component (a) and (1 ) And (2) components can be agglomerated. Examples of the coagulation liquid include the non-solvents described above. The coagulation solution can be obtained by adding a pH adjuster such as acetic acid.
[0053] ポリマーブレンドを含む成形品もまた、公知の方法により調製することができる。 [0054] 繊維を調製する場合、例えば、ポリ口タキサン含有溶液を紡糸ノズルから、凝固浴 中に吐出し、フィラメント状に凝集させ、繊維として浴から引き取る方法を採用すること ができる。また、ポリ口タキサン含有溶液を紡糸ノズルから、ー且、空気中に吐出し、 形成されたフィラメント状溶液流を凝固液の浴に入れて凝集させてもよい。 [0053] Molded articles containing polymer blends can also be prepared by known methods. [0054] When preparing the fiber, for example, a method in which a polymouth taxane-containing solution is discharged from a spinning nozzle into a coagulation bath, aggregated in a filament form, and taken out from the bath as a fiber can be employed. Alternatively, the polymouth taxane-containing solution may be discharged from a spinning nozzle into the air, and the formed filamentous solution stream may be put into a coagulating liquid bath to be agglomerated.
[0055] フィルムを調製する場合は、例えば、ポリ口タキサン含有溶液をキャスティングし、次 V、でこれを凝固液に接触させて凝集させフィルムとする、キャスティング法を採用する ことができる。また、インフレーション法によりブローンフィルムとして調製することも可 能である。  [0055] In the case of preparing a film, for example, a casting method can be employed in which a polymouth taxane-containing solution is cast and then brought into contact with a coagulation liquid in the next step V to agglomerate to form a film. It can also be prepared as a blown film by the inflation method.
実施例  Example
[0056] 以下、実施例に基づいて、本発明をさらに詳細に説明するが、本発明は本実施例 に限定されるものではない。  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples.
[0057] 実施例において、原料は以下を用いた。 In the examples, the following materials were used.
(1)ポリ口タキサン (PR)は、以下のとおりであり、アドバンスド 'ソフトマテリアルズ株式 会社より同等品を購入可能である。  (1) Poly mouth taxane (PR) is as follows, and equivalent products can be purchased from Advanced Soft Materials Co., Ltd.
—直鎖状分子は PEGであり、平均重合分子量 35, 000である。末端にアミド結合 を介してァダマンタン基を有する。  —The linear molecule is PEG with an average molecular weight of 35,000. It has an adamantane group via an amide bond at the end.
一環状分子は α— CDであり、包接している CD数は 90〜: LOO個(包接率約 22〜2 5%)である。  The monocyclic molecule is α-CD, and the number of CDs included is 90-: LOO (inclusion rate is about 22-25%).
(2)セルロースは、 Whatman社製、商品名 CF11の微結晶性セルロースである。 (2) Cellulose is microcrystalline cellulose manufactured by Whatman and trade name CF11.
(3) N, N ジメチルァセトアミド(DMAc)は、和光純薬社製の実験グレードの試薬 であり、予めモレキュラーシーブ 4A (和光純薬社製)を入れて、一日放置し、微量の 水分を除去したものである。 (3) N, N dimethylacetamide (DMAc) is an experimental grade reagent manufactured by Wako Pure Chemical Industries, Ltd. In advance, a molecular sieve 4A (manufactured by Wako Pure Chemical Industries, Ltd.) is placed in advance and left for a day. The water is removed.
(4)無水塩化リチウム (LiCl)は、和光純薬社製の実験グレードの試薬を、予め 105 °Cで 2時間以上乾燥させたものである。  (4) Anhydrous lithium chloride (LiCl) is an experimental grade reagent manufactured by Wako Pure Chemical Industries, which has been dried at 105 ° C for 2 hours or more in advance.
[0058] 例 1:ポリマーブレンドを含む成形品の調製  [0058] Example 1: Preparation of molded article containing polymer blend
4 メチルモルホリンー4 ォキシドー水和物(NMMO) 9. 5gを、 90°Cにカロ熱して 溶融させて、粉砕した PR250mgと没食子酸プロピル(PG) 5mgを添カ卩し 100°Cで 3 0分加熱した。次いでセルロース 250mgを添カ卩し、 100°Cで更に 1時間攪拌したとこ ろ、やや粘稠な褐色の溶液が得られた。 4 Methylmorpholine-4-oxide hydrate (NMMO) 9.5 g was melted by heating to 90 ° C, and crushed PR 250 mg and propyl gallate (PG) 5 mg were added. Heated for minutes. Next, add 250 mg of cellulose and stir at 100 ° C for an additional hour. A slightly viscous brown solution was obtained.
上記で得られた溶液を、 105°Cの真空乾燥機で、真空下に 10〜15分間置き、脱 泡した。溶液 5mlを、高温のうちにテフロン製シャーレ( φ 50mm)にキャスティングし 、さらに 105°Cで 10分保持した後、デシケータ内で室温に冷却し固化させた。固化し た試料を、メタノール Z水(75Z25、 v/v)の混合溶媒に浸して、 NMMO及び PGを 溶出させた。混合溶媒で洗浄を 2回繰り返した後、イオン交換水で洗浄し、白濁した ゲル状の成形品を得た。  The solution obtained above was deaerated by placing it in a vacuum dryer at 105 ° C. under vacuum for 10 to 15 minutes. 5 ml of the solution was cast in a Teflon petri dish (φ50 mm) at a high temperature and further maintained at 105 ° C. for 10 minutes, and then cooled to room temperature in a desiccator and solidified. The solidified sample was immersed in a mixed solvent of methanol Z water (75Z25, v / v) to elute NMMO and PG. Washing with the mixed solvent was repeated twice, followed by washing with ion-exchanged water to obtain a white turbid gel-like molded product.
[0059] 例 2:ポリマーブレンドを含むフィルムの調製 [0059] Example 2: Preparation of a film containing a polymer blend
NMM018gを、 90°Cに加熱して溶融させて、 PRlg及びセルロース lgを添カ卩した 。マグネチックスターラーで攪拌したところ、これらは溶解し、半透明の粘稠な溶液が 得られたが、一部は溶解せずに容器の底に残存した。  NMM018g was melted by heating to 90 ° C., and PRlg and cellulose lg were added. When stirring with a magnetic stirrer, these dissolved and a translucent viscous solution was obtained, but some remained undissolved at the bottom of the container.
上記で得られた溶液を、ガラス板状にキャスティングし、その後、メタノール Z水(75 Z25、 v/v)で洗浄することにより、 NMMOを溶出させ、 PRとセルロースとのポリマー ブレンドを凝集させて、やや白色半透明のゲル状のフィルムを得た。  The solution obtained above is cast into a glass plate and then washed with methanol Z water (75 Z25, v / v) to elute NMMO and agglomerate the polymer blend of PR and cellulose. A slightly white translucent gel-like film was obtained.
[0060] 例 3:ポリマーブレンドを含む繊維の調製 [0060] Example 3: Preparation of fiber containing polymer blend
セルロース 10gを、 DMAc200mlに添カ卩して攪拌し、懸濁させた後、 130°Cで 2時 間加熱した。加熱をやめ、 100°Cに降温させた後、 LiCl 10gを添加して攪拌し、室 温まで冷却しながら攪拌を続け、セルロース濃度が約 5重量%の透明な溶液(1)を 得た。  10 g of cellulose was added to 200 ml of DMAc, stirred and suspended, and then heated at 130 ° C. for 2 hours. After heating was stopped and the temperature was lowered to 100 ° C., 10 g of LiCl was added and stirred, and stirring was continued while cooling to room temperature to obtain a transparent solution (1) having a cellulose concentration of about 5% by weight.
[0061] L1C14. 5gを、 DMAc 45. 5gに添カ卩し、容器を密封して、 60°Cの油浴中で攪拌 し、 LiClを完全に溶解させた。その後、ポリ口タキサン 5gを添加し、引き続き、 60°C油 浴中で撹拌を続けた。ポリ口タキサンを完全に溶解させた後、室温まで冷却し、ポリ口 タキサン濃度が約 10重量%の溶液(2)を得た。  [0061] 14.5 g of L1C was added to 45.5 g of DMAc, the container was sealed, and the mixture was stirred in an oil bath at 60 ° C to completely dissolve LiCl. Thereafter, 5 g of polypolytaxane was added, and the stirring was continued in a 60 ° C oil bath. After completely dissolving the polymouth taxane, it was cooled to room temperature to obtain a solution (2) having a polymouth taxane concentration of about 10% by weight.
[0062] 溶液(1)と溶液 (2)を、体積比で、 1 : 2で混合し、ポリ口タキサン含有溶液を得た。  [0062] The solution (1) and the solution (2) were mixed at a volume ratio of 1: 2 to obtain a solution containing a poly (taxane) taxane.
ポリ口タキサン含有溶液を注射器で、凝固浴であるメタノールを満たしたビーカー中 に押出し、ポリマーブレンドをフィラメント状に凝固させ、底面に沈殿させた。これを遠 心チューブに巻き取り、 60°Cで加熱し、乾燥させたところ、太さ約 180 /z mの繊維が 得られた。 溶液(1)と溶液 (2)とを、 1: 1、 2 : 1の体積比で混合し、それぞれポリ口タキサン含 有溶液を得て、上記と同様の方法で紡糸したところ、太さ約 180 mの繊維が得られ た。 The solution containing the polymouth taxane was extruded with a syringe into a beaker filled with methanol as a coagulation bath, and the polymer blend was coagulated into filaments and precipitated on the bottom surface. This was wound up on a centrifuge tube, heated at 60 ° C. and dried to obtain a fiber having a thickness of about 180 / zm. When the solution (1) and the solution (2) were mixed at a volume ratio of 1: 1, 2: 1, respectively, polypolytaxane-containing solutions were obtained and spun by the same method as described above. A 180 m fiber was obtained.
上記の繊維は、いずれもしなやかであり、顕微鏡写真で観察すると、均一な構造で あることがわかった(図 1)。  All of the above fibers were supple, and when observed with a photomicrograph, they were found to have a uniform structure (Figure 1).
[0063] 例 4:ポリマーブレンドを含む繊維の調製と物性の評価 [0063] Example 4: Preparation of fiber containing polymer blend and evaluation of physical properties
溶液(1)及び溶液(2)を、ポリ口タキサンとセルロースの重量比が下記表 1の割合と なるように混合してポリ口タキサン含有溶液を得た。次いで、これらの溶液を用いて、 例 3と同様にして、実施例 4— 1〜4— 3の繊維を得た (太さ約 180 m)。  The solution (1) and the solution (2) were mixed so that the weight ratio of the polymouth taxane to cellulose was the ratio shown in Table 1 below to obtain a polymouth taxane-containing solution. Then, using these solutions, fibers of Examples 4-1 to 4-3 were obtained in the same manner as in Example 3 (thickness: about 180 m).
また、溶液(1)のみを用いて、例 3と同様にして、セルロース単独の比較例 1の繊維 を得た(太さ約 180 m)。  In addition, only the solution (1) was used in the same manner as in Example 3 to obtain a fiber of Comparative Example 1 containing cellulose alone (thickness: about 180 m).
さらに、ポリ口タキサンの添加量を 10gとした以外は溶液(2)と同様にしてポリ口タキ サン含有溶液を得た。次いで、この溶液を用いて、例 3と同様にして (ただし、径が小 さいノズルを使用して押出しを実施した)、ポリ口タキサン単独の比較例 2の繊維を得 た(太さ約 90 /ζ πι)。  Further, a solution containing a poly (taxane) taxan was obtained in the same manner as in the solution (2) except that the amount of poly (taxane) added was 10 g. Then, using this solution, a fiber of Comparative Example 2 containing only a polymouth taxane was obtained (thickness of about 90) in the same manner as in Example 3 (extruding was performed using a nozzle having a small diameter). / ζ πι).
[0064] 例4 1〜4 3、比較例 1〜2の各繊維について、レオメータ RSAIII (ΤΑインスッ ルメント社製)を用いて、スパン長 15mm、伸長速度 0. 15mmZ秒の条件で、ヤング 率及び引張り強度を測定したところ、下記表の値を示した。  [0064] For each of the fibers of Examples 4 to 4 3 and Comparative Examples 1 and 2, using a rheometer RSAIII (manufactured by Sakai Instruments), the Young's modulus and When the tensile strength was measured, the values shown in the following table were shown.
[0065] 表 1  [0065] Table 1
Figure imgf000014_0001
Figure imgf000014_0001
*比較例 1 、 例 4— 1 ~ 4— 3は、 それぞれ 5個の試料について測定を実施し、 平均値を算出。 比較例 2は、 * Comparative Example 1 and Examples 4–1 to 4–3 each measured 5 samples and calculated the average value. Comparative Example 2
1 0個の試料について測定を実施し、 平均値を算出。 Measurement was performed on 10 samples, and the average value was calculated.
[0066] 上記表 1より、ポリ口タキサンとのブレンドの繊維とすることにより、ヤング率及び引張 り強度の値が変化することがわかる。特に、例4 1〜4 2は、セルロース単独の比 較例 1及びポリ口タキサン単独の比較例 2のいずれよりも大きいヤング率及び引張り 強度を示した。 産業上の利用可能性 [0066] From Table 1 above, it can be seen that the Young's modulus and tensile strength values are changed by using a fiber blended with a polyortaxane. In particular, Examples 41 and 42 showed Young's modulus and tensile strength that were higher than those of Comparative Example 1 of cellulose alone and Comparative Example 2 of polyortaxane alone. Industrial applicability
本発明は、繊維及びフィルムに成形することが可能な新たな素材を提供するもので ある。本発明は、ポリ口タキサンの素材としての可能性を広げるとともに、近年、資源 枯渴問題の点力も脚光をあびるセルロース、キチン、キトサン等の天然物を用いた成 形品の形状や物性の設計への応用が期待できる。  The present invention provides a new material that can be formed into fibers and films. The present invention expands the possibilities as a raw material for poly-oral taxanes, and in recent years, the shape and physical properties of molded products using natural products such as cellulose, chitin, chitosan, etc., which are also attracting attention as a resource exhaustion problem. Application to can be expected.

Claims

請求の範囲 [1] (1)ポリ口タキサン、並びに (2) (a)第三級アミンォキシド又はその水和物;アミド及びハロゲン化金属;並びにィ オン性液体カゝらなる群より選択される溶媒の少なくとも 1種に溶解しうる高分子材料 力もなるポリマーブレンド。 [2] (a)第三級アミンォキシド又はその水和物;アミド及びハロゲン化金属;並びにィォ ン性液体力 なる群より選択される溶媒の少なくとも 1種、 Claims [1] selected from the group consisting of (1) a polyoral taxane, and (2) (a) a tertiary amine oxide or hydrate thereof; an amide and a metal halide; and an ionic liquid salt A polymer blend that can dissolve in at least one solvent. [2] (a) tertiary amine oxide or hydrate thereof; amide and metal halide; and at least one solvent selected from the group consisting of ionic liquid forces,
(1)ポリ口タキサン、  (1) poly oral taxane,
(2) (a)成分に溶解しうる高分子材料  (2) Polymer material that can be dissolved in component (a)
を含む、ポリ口タキサン含有溶液を用いて得られる、請求項 1記載のポリマーブレンド  A polymer blend according to claim 1 obtained using a polymouth taxane-containing solution comprising
[3] ポリ口タキサン含有溶液から、(1)及び(2)成分を凝集させることにより得られる、請 求項 2記載のポリマーブレンド。 [3] The polymer blend according to claim 2, which is obtained by agglomerating the components (1) and (2) from a polymouth taxane-containing solution.
[4] (1)成分が、 (X—シクロデキストリンカ、ポリエチレングリコールを包接する擬ポリロタ キサンにブロック基を配置したポリ口タキサンである、請求項 1〜3のいずれか 1項記 載のポリマーブレンド。 [4] The polymer according to any one of claims 1 to 3, wherein the component (1) is a poly (oral taxane) in which a blocking group is arranged in a pseudopolyrotaxane that includes (X-cyclodextrinca and polyethylene glycol). Blend.
[5] (2)成分が、セルロース、キチン、キトサン、動物繊維又は合成ポリマーである、請 求項 1〜4のいずれか 1項記載のポリマーブレンド。  [5] The polymer blend according to any one of claims 1 to 4, wherein the component (2) is cellulose, chitin, chitosan, animal fiber or a synthetic polymer.
[6] (2)成分が、セルロースである、請求項 5記載のポリマーブレンド。 6. The polymer blend according to claim 5, wherein the component (2) is cellulose.
[7] (a)成分が、 N メチルモルホリン N ォキシド' 1水和物である、請求項 1〜6の いずれ力 1項記載のポリマーブレンド。  [7] The polymer blend according to any one of claims 1 to 6, wherein the component (a) is N-methylmorpholine N-oxide 'monohydrate.
[8] (a)成分が、 N, N ジメチルァセトアミド、 N—メチル—2 ピロリドン及び 1, 3 ジ メチル 2—イミダゾリジノン力もなる群より選択される少なくとも 1種並びに塩化リチウ ムである、請求項 1〜6のいずれか 1項記載のポリマーブレンド。 [8] The component (a) is at least one selected from the group consisting of N, N dimethylacetamide, N-methyl-2 pyrrolidone and 1,3 dimethyl 2-imidazolidinone and lithium chloride. The polymer blend according to any one of claims 1 to 6.
[9] (a)成分が、 N, N'—ジアルキルイミダゾリゥムの塩化物塩及び N—アルキルピリジ[9] The component (a) is a chloride salt of N, N'-dialkylimidazole and N-alkylpyridyl
-ゥムの塩ィ匕物塩力もなる群より選択される少なくとも 1種である、 1〜6のいずれか 1 項記載のポリマーブレンド。 The polymer blend according to any one of 1 to 6, which is at least one selected from the group consisting of salt and salt strength of um.
[10] 請求項 1〜9のいずれか 1項記載のポリマーブレンドを含む成形品。 [11] 繊維又はフィルムである、請求項 10記載の成形品。 [10] A molded article comprising the polymer blend according to any one of claims 1 to 9. [11] The molded article according to claim 10, which is a fiber or a film.
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