WO2010146873A1 - Fibres contenant de l'amylose, leur procédé de production et leur utilisation - Google Patents

Fibres contenant de l'amylose, leur procédé de production et leur utilisation Download PDF

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WO2010146873A1
WO2010146873A1 PCT/JP2010/004067 JP2010004067W WO2010146873A1 WO 2010146873 A1 WO2010146873 A1 WO 2010146873A1 JP 2010004067 W JP2010004067 W JP 2010004067W WO 2010146873 A1 WO2010146873 A1 WO 2010146873A1
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Prior art keywords
amylose
rayon fiber
containing rayon
substance
rayon
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Japanese (ja)
Inventor
井上修
吉川政敏
高久三枝子
三瓶春代
寺田喜信
鷹羽武史
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Ezaki Glico Co Ltd
Omikenshi Co Ltd
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Ezaki Glico Co Ltd
Omikenshi Co Ltd
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Priority to JP2011519577A priority Critical patent/JP5496194B2/ja
Publication of WO2010146873A1 publication Critical patent/WO2010146873A1/fr
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath

Definitions

  • the present invention relates to a functional rayon fiber containing amylose, a method for producing the same, and use thereof.
  • Plant starch is composed of amylose and amylopectin.
  • normal corn starch is composed of about 20% amylose and about 80% amylopectin.
  • Natural amylose contained in plant starch is a polysaccharide in which many glucoses are mainly linked by ⁇ -1,4 glucoside bonds, but it is known that it has a slight branched structure consisting of ⁇ -1,6 glucoside bonds. It has been.
  • amylopectin is a macromolecule in which a short amylose chain having a degree of polymerization of about 20 is bound in a tuft-like manner through ⁇ -1,6-glucoside bonds.
  • the linear ⁇ -1,4 glucan chain that constitutes amylose has a characteristic of forming a helical structure, and has long had a function of incorporating various substances into the helical structure (called an inclusion function).
  • an inclusion function a function of incorporating various substances into the helical structure.
  • Amylose is a polysaccharide with a unique function of inclusion, but it is very difficult to separate it from amylopectin in starch, so there is no production of pure amylose on an industrial scale. Industrial use is not progressing. In recent years, it has become possible to synthesize enzymatically pure amylose (Patent Document 1), and research on the use of amylose is proceeding (Patent Document 2). For example, Patent Document 3 discloses molded products such as fibers and films made of enzyme-synthesized amylose. Molded products made of these amyloses are easily biodegradable and biocompatible because they are easily degraded by microorganisms and amylases in animal bodies.
  • Patent Document 3 discloses that a molded product made of amylose is used for applications that require biodegradability.
  • fibers composed only of amylose are not suitable for uses such as repeated use and repeated washing because the biodegradability is too good.
  • biodegradability is described as being controllable by chemical modification, chemical modification remarkably suppresses the inclusion function of amylose, and thus is not suitable for applications utilizing the inclusion function of amylose.
  • chemical fibers such as polyester fibers are mainly used as the fibers.
  • amylose cannot be dissolved in the solvent of the conventional chemical fiber material, amylose cannot be contained in the chemical fiber. Even if they can be contained, the chemical fiber and amylose are not compatible, so they cannot be mixed in molecular units and phase separated.
  • cellulose is a polysaccharide constituting the plant cell wall and is a polysaccharide in which many glucoses are linked by ⁇ -1,4 glucoside bonds.
  • Cellulose is a much more stable polysaccharide than starch, and is a major raw material such as clothing, non-woven fabric, and paper. However, cellulose does not have an inclusion function.
  • Patent Document 4 discloses a method in which an aqueous amylose solution is applied to a nonwoven fabric made of cellulose fibers, and the cellulose fibers are coated with amylose. Although this method is easy to operate and practical, amylose adhering to the cellulose surface is easily lost by operations such as washing, and therefore has a problem that it cannot withstand repeated use.
  • One of the cellulose fibers is rayon.
  • Rayon is fiberized while regenerating cellulose from a cellulose solution (viscose) dissolved using carbon disulfide.
  • Rayon can be made to contain functional substances in the rayon by adding various functional substances to the viscose because of its manufacturing characteristics, and as a result, the function can be given to the rayon.
  • rayon fiber containing chitosan (Patent Document 5), rayon fiber containing composite metal oxide fine particles (Patent Document 6), rayon containing Bichotan charcoal fine particles (Patent Document 7), anionic polymer
  • the contained rayon fiber (patent document 8) etc. are disclosed.
  • the molecular weight of the polymer substance is suitably 10,000 to 500,000 from the viewpoint of yield in the rayon.
  • the technique described in Patent Document 8 merely uses a polymer substance to retain the ionic functional group in the rayon, and the structure of the polymer substance in the rayon is not a problem.
  • a high molecular weight material such as amylose has functionality
  • the above-mentioned polymer material is not covered by the rayon and the functionality is not exhibited, and the structural change of the polymer material may cause this. In some cases, the function is not fully exhibited. This structural change of the polymer substance varies depending on the kind of polymer substance and the production method, and therefore it is very difficult to predict the result.
  • Patent Document 8 aims to prevent a decrease in the antibacterial action due to the quaternary ammonium salt compound being removed by repeated washing, and the subject is completely different from the present invention.
  • the antibacterial agent is bound by ionic bond, whereas in the present invention, the antibacterial agent is included in amylose. Therefore, the antibacterial agent retention method is completely different.
  • the ionic bond can bind the antibacterial agent only to a certain part of the ion, in the present invention, since the antibacterial agent can be included in various parts of the amylose chain, a substance that binds to the quaternary ammonium salt in the fiber If the content of amylose is the same, a larger amount of antibacterial agent than before can be bound.
  • Cyclodextrin is known as a compound having an inclusion ability.
  • cyclodextrin has a small molecular weight and dissolves in water, in the case of wet spinning viscose rayon, cyclodextrin is eluted into the spinning bath when fiberized and yield in the fiber is poor. Even if a small amount of cyclodextrin can be contained in the rayon fiber, the cyclodextrin is easily eluted from the fiber, so that the resulting fiber is inferior in stability.
  • Non-Patent Document 1 a method of binding cyclodextrin to the fiber surface by chemical bonding is disclosed.
  • this method inclusion ability can be imparted only to the fiber surface.
  • this fiber is exposed to an acid or alkali solution, there is a problem that the chemical bond is broken and the cyclodextrin on the fiber surface is eluted, and the inclusion ability is easily lost.
  • Patent Document 10 a method of obtaining a fiber by mixing a conjugate obtained by bonding cyclodextrin to the end of a polyester polymer by chemical bonding with a thermoplastic resin is disclosed (Patent Document). 10).
  • the cyclodextrin is bound only to the polymer end, the amount of cyclodextrin bound is small, and the cyclodextrin coated with the polymer cannot exert the inclusion ability. There is a problem that is limited. If an attempt is made to increase the amount of cyclodextrin bonded by this method, the degree of polymerization of the polymer must be reduced, resulting in a problem that the fiber strength is insufficient.
  • Patent Document 11 a method of chemically bonding a plurality of cyclodextrins to a polymer molecule is also disclosed (Patent Document 11).
  • this method also requires a complicated process of synthesizing a cyclodextrin derivative and further carrying out a polymerization reaction, which takes time for synthesis and is inefficient. Furthermore, it is unclear whether the obtained polymer can be made into fiber and whether it has sufficient inclusion ability after molding.
  • the function of the guest material is manifested by releasing the guest material due to a change in the external environment.
  • cyclodextrin a compound with conventional clathrate ability, guest substances are released due to changes in humidity, etc., but cyclodextrin has too much clathrate power, so the amount released is small, and as a result, the function of the guest substance is fully expressed May not.
  • amylose When amylose is used as a functional ingredient, natural amylose is completely dissolved under the alkaline conditions at the time of rayon production, even if natural amylose is added to rayon in the same manner as described in Patent Documents 5 to 8. do not do. As a result, nozzle clogging occurred during the production of rayon, and an amylose-containing rayon could not be produced.
  • JP-T-2004-526463 International Publication No. 2006/082968 Pamphlet International Publication No. 02/006507 Pamphlet JP 2008-37833 A JP-A-8-92820 JP 2004-162245 A JP 2001-98412 A JP-A-7-173711 JP 2005-503476 A Japanese Patent Laid-Open No. 08-100027
  • the present invention intends to solve the above problems.
  • the present invention aims to develop a fiber with an amylose inclusion function, and more specifically to develop a functional rayon fiber with an amylose inclusion function.
  • the functional rayon fiber of the present invention stably retains amylose without greatly changing the physical properties of the rayon fiber except that the inclusion function of amylose is given. It does not substantially elute and can withstand repeated use. Furthermore, since the functional rayon fiber of the present invention contains amylose in a state in which the inclusion function can be exerted, it is possible to provide additional function to the fiber by inclusion in various types of guest substances and inclusion in amylose. Can do.
  • rayon is most suitable for obtaining a fiber having an inclusion function of amylose.
  • amylose dissolved in alkali is mixed with viscose and dispersed in the mixture, and then the mixture is made into fibers, so that amylose is not substantially eluted and the inclusion action can be exerted.
  • amylose-containing rayon fiber in which amylose was dispersed in rayon fiber in the state could be produced, and based on this, the present invention was completed.
  • the obtained fiber hardly changed the physical properties of the original rayon fiber except that the inclusion function of amylose was given.
  • amylose-containing rayon fiber of the present invention has a remarkable effect that it can withstand repeated use. Furthermore, by heating the rayon fiber of the present invention in an aqueous solution containing an organic solvent, the inclusion function of amylose in the rayon can be further increased. Thus, the present inventors have completed the present invention by developing a functional rayon fiber having superior properties and a method for producing the same.
  • the present invention provides, for example: (Item 1) A method for producing amylose-containing rayon fiber, A step of mixing an alkaline aqueous solution of amylose and viscose to obtain a mixed solution; and a step of spinning the mixed solution to obtain amylose-containing rayon fiber,
  • the method wherein the amylose is enzyme-synthesized amylose having a weight average molecular weight of about 3 ⁇ 10 4 or more and about 2 ⁇ 10 5 or less.
  • the method includes a step of contacting the amylose-containing rayon fiber with a guest substance to include the guest substance in amylose of the amylose-containing rayon fiber, wherein the guest substance is a substance other than iodine and polyiodide ions.
  • the guest substance is selected from the group consisting of a bactericidal agent, an antibacterial agent, an insect repellent component, an odor component, a physiologically functional material, a UV absorbing material, a cosmetic component, a colorant, a dye, a deodorizing component, and an antifungal component; Item 4.
  • the method according to any one of Items 1 to 3.
  • Amylose-containing rayon fiber having the ability to include a guest substance, wherein amylose in the rayon fiber is not substantially eluted by washing and is dispersed in the rayon fiber.
  • an enzyme-synthesized amylose having a weight average molecular weight of about 3 ⁇ 10 4 or more and about 2 ⁇ 10 5 or less, wherein the amylose does not include a guest substance.
  • Amylose-containing rayon fiber wherein the amylose in the rayon fiber is not substantially eluted by washing and is dispersed in the rayon fiber, and the amylose has a weight average molecular weight of about 3
  • An amylose-containing rayon fiber which is an enzyme-synthesized amylose of ⁇ 10 4 or more and about 2 ⁇ 10 5 or less, wherein the amylose includes a guest substance other than iodine and polyiodide ions.
  • (Item 21) A method for trapping a chemical substance in a fiber in order to concentrate, recover, remove or isolate the chemical substance, A step of bringing the chemical substance into inclusion in the amylose by bringing the solution or gas containing the chemical substance into contact with the amylose-containing rayon fiber according to item 9 or 10; A method of inclusion, wherein the chemical is a substance other than iodine and polyiodide ions.
  • (Item 23) A product obtained from a woven fabric, a knitted fabric, a non-woven fabric, or paper, containing the amylose-containing rayon fiber according to any one of Items 9 to 20.
  • (Item 24) A deodorizing product comprising the amylose-containing rayon fiber according to any one of Items 9, 10 and 18.
  • the amylose-containing rayon fiber of the present invention stably retains amylose, and does not elute amylose even in operations such as washing and can withstand repeated use. Furthermore, the amylose-containing rayon fiber is contained in a state in which amylose can exert an inclusion function, and an additional function can be imparted to the fiber by adding various guest substances. For example, an amylose-containing rayon fiber encapsulated with a UV absorber such as nonylphenol exhibits a very excellent UV protection effect.
  • the inclusion ability of the amylose-containing rayon fiber of the present invention can be remarkably increased compared to the sum of the inclusion ability of pure amylose and the inclusion ability of pure rayon fiber not contained in the rayon fiber.
  • FIG. 1 is a graph showing the results of the ultraviolet absorption spectrum obtained in Example 11.
  • the vertical axis represents intensity (Int.)
  • the horizontal axis represents wavelength (Wavelength).
  • the solid line indicates the nonylphenol-encapsulated amylose-containing non-woven fabric
  • the wavy line indicates the control non-woven fabric treated with nonylphenol.
  • FIG. 2 is a graph showing the menthol retention stability of a thermal bond nonwoven fabric containing rayon containing menthol inclusion amylose.
  • FIG. 3 is a graph showing sustained release of menthol from a menthol-encapsulated amylose-containing rayon-blown thermal bond nonwoven fabric.
  • Amylose is a sugar having D-glucose as a constituent unit and mainly linked by ⁇ -1,4-glucoside bonds. Is a substantially linear polysaccharide having at least two disaccharide units. In the amylose molecule used in the present invention, the saccharide units are preferably linked only by ⁇ -1,4-glucoside bonds. “Linear” means that there is no branching. The branch is formed, for example, by a structure in which glucose residues are linked to three positions of 1-position, 4-position and 6-position of one glucose residue. “Substantially linear” includes those that are completely linear and those that contain a small number of branches.
  • the number of branches is preferably about 100 or less per 10,000 glucose residues, more preferably about 50 or less, more preferably about 10 or less, particularly preferably about 1 or less, and most preferably 0. .
  • Amylose is synonymous with linear ⁇ -glucan and ⁇ -1,4-glucan. Among linear amyloses, amylose having no branching is referred to as completely linear amylose.
  • Amylose may contain relatively few ⁇ -1,6-glucoside bonds.
  • the number of ⁇ -1,4-glucoside bonds when the number of ⁇ -1,6-glucoside bonds is 1 is preferably about 100 or more, more preferably about 200 or more. More preferably, it is about 300 or more, particularly preferably about 400 or more, and most preferably about 500 or more.
  • amylose used in the present invention preferably, there is no particular upper limit to the number of ⁇ -1,4-glucoside bonds when the number of ⁇ -1,6-glucoside bonds is 1, for example, about 15000 or less, about It may be 10,000 or less, about 5000 or less, about 4000 or less, about 3000 or less, about 2000 or less, about 1000 or less, about 500 or less, about 400 or less, about 300 or less.
  • the dispersity of amylose used in the present invention is preferably 3.0 or less. Except for special cases such as proteins, a high molecular compound has a molecular weight that is not single but has a certain range regardless of whether the high molecular compound is natural or non-natural. Therefore, in order to show the degree of dispersion of the molecular weight of the polymer compound, the dispersion degree Mw / Mn is usually used in the field of polymer chemistry.
  • the degree of dispersion Mw / Mn is represented by the ratio of the number average molecular weight Mn to the weight average molecular weight Mw (that is, Mw ⁇ Mn).
  • the degree of dispersion is an indicator of the breadth of the molecular weight distribution of the polymer compound. In the case of a polymer compound having a completely single molecular weight, Mw / Mn is 1, and Mw / Mn becomes a value larger than 1 as the molecular weight distribution increases.
  • the dispersity of the amylose used in the present invention is more preferably about 2.8 or less, more preferably about 2.5 or less, still more preferably about 2.3 or less, and still more preferably About 2.0 or less, even more preferably about 1.5 or less, and most preferably about 1.2 or less.
  • the number of sugar units contained in one molecule of ⁇ -1,4-glucan is called the degree of polymerization.
  • degree of polymerization refers to the weight average degree of polymerization unless otherwise specified.
  • the weight average degree of polymerization is calculated by dividing the weight average molecular weight by 162.
  • the “average molecular weight” refers to a weight average molecular weight unless otherwise specified.
  • Natural starch is usually composed of a mixture of both amylose (a polymer having a structure in which glucose is linearly bonded) and amylopectin (a tufted polymer in which amylose is branched).
  • Amylose contained in natural starch usually has a molecular weight distribution (Mw / Mn) wider than 3.0, (i) a low molecular weight amylose that is easily crystallized, (ii) a high molecular weight substance that is easily dissolved in water, and (iii) Since amylose having an intermediate molecular weight and easily gelled is mixed, the amylose characteristics of other molecular weight regions are mutually inhibited. In addition, natural amylose often contains slight branching.
  • amylose isolated from natural starch when used, the properties of the product obtained are also inferior. Moreover, when a high concentration alkaline solution is prepared using amylose having a large molecular weight, the viscosity of the alkaline solution increases, so that this alkaline solution is inferior in processing characteristics in fiber production and the like. Therefore, natural amylose is not preferred. That is, amylose other than natural amylose is preferably used in the present invention.
  • the amylose used in the present invention is preferably enzymatically synthesized amylose.
  • Enzymatic amylose refers to amylose obtained by linking sugar units to a primer using an enzyme.
  • the enzyme-synthesized amylose used in the present invention can be produced by any enzyme synthesis method known in the art.
  • An example of such an enzyme synthesis method is a method using glucan phosphorylase.
  • Phosphorylase is an enzyme that catalyzes a phosphorolysis reaction.
  • amylose enzymatic synthesis methods examples include the following: (1) ⁇ -Glucan phosphorylase (GP) (eg, derived from potato) is used to convert ⁇ -glucose-1-phosphate glucosyl group to a primer such as maltoheptaose. A method of synthesizing ⁇ -1,4-glucan chains by transfer; (2) Method of synthesizing ⁇ -1,4-glucan chain by simultaneously acting sucrose phosphorylase and glucan phosphorylase using primer, sucrose and inorganic phosphate or glucose-1-phosphate as a substrate (hereinafter referred to as SP-GP method) (Waldmann, H.
  • SP-GP method sucrose and inorganic phosphate or glucose-1-phosphate
  • Primer used in the production of enzymatically synthesized amylose refers to a sugar chain molecule that acts as a starting material in the synthesis of ⁇ -1,4 glucan chains.
  • primers include any saccharide to which a saccharide unit can be added by ⁇ -glucan phosphorylase.
  • the primer include maltooligosaccharide.
  • a method for producing enzyme-synthesized amylose is described, for example, in JP-T-2004-526463.
  • Enzyme-synthesized amylose has the advantage that it does not contain branches and has a low degree of dispersion, that is, has a uniform molecular weight.
  • the average molecular weight (weight average molecular weight) of the amylose used in the present invention is preferably about 3 ⁇ 10 4 or more, and more preferably about 3 ⁇ 10 4 or more in order to realize the property of having an inclusion force when contained in the rayon. 4 ⁇ 10 4 or more, particularly preferably about 4.5 ⁇ 10 4 or more, and most preferably about 5 ⁇ 10 4 or more.
  • the average molecular weight of amylose used in the present invention is preferably about 2 ⁇ 10 5 or less, more preferably about 1.5 ⁇ 10 5 or less, and most preferably about 1.2 ⁇ 10 5 or less. .
  • the average molecular weight of amylose is too small, there is a problem that the inclusion force of amylose is not sufficiently exhibited in the rayon. If the average molecular weight of amylose is too large, it may not be incorporated well into rayon, the inclusion power of amylose will be impaired, or the filterability of viscose will deteriorate, making it difficult to stably produce rayon fiber. There is.
  • the average molecular weight of enzyme-synthesized amylose can be adjusted by changing the ratio of the sucrose concentration and the primer concentration used for enzyme synthesis.
  • sucrose concentration is constant, the lower the primer concentration, the higher the average molecular weight of the resulting amylose.
  • a person skilled in the art can easily synthesize amylose having a target molecular weight by reading Patent Document 1 and the synthesis examples of the present application.
  • Viscose can be produced by methods known in the art. For example, sulfite pulp is immersed in 17-18% caustic soda solution. Pulp becomes alkali fiber and expands 4-5 times in volume. This is squeezed to squeeze out excess alkali, put in a pulverizer, pulverize and stir. This is aged and reacted with carbon disulfide to form xanthates. A solution obtained by adding a dilute caustic soda solution to xanthate and making it liquid is called viscose.
  • the substance (also referred to as guest substance) included in amylose can be any substance as long as it can be included in amylose.
  • Guest substances can be molecules, compounds, atoms, ions, and the like.
  • the guest material is a material other than iodine and polyiodide ions.
  • guest substances include: (a) fungicides and antibacterial agents; (b) insect repellent components; (c) odor components; (d) components to be stabilized; (e) sustained release components; (G) Cosmetic ingredients; (h) Colorants or dyes; (i) Deodorant ingredients; (j) Antifungal ingredients.
  • Examples of (a) fungicides and antibacterial agents include, for example, penicillin, ampicillin, amoxicillin, cephalosporin, tetracycline, oxytetracycline, chlortetracycline, methicillin, sodium colistin methanesulfonate, carbenicillin sodium, gentamicin, erythromycin, azithromycin, Roxithromycin, Clarithromycin, Terythromycin, Josamycin, Spiramycin, Leucomycin, Midecamycin, Rokitamycin, Midecamycin, Tobramycin, Kanamycin, Cefuroxime Sodium, Meropenem, Netilmycin, Sisomycin, Ceftibutene, Tobramycin, Doxorubicin, Astromycin Fetamethopivoxil, nalidixic acid, pyrometic acid, Pemidic acid, sinoxane, norfloxacin, ofloxacin, enoxacin, ciprofloxacin, tosufloxaci
  • Cationic fungicides alkylpyridinium such as cetylpyridinium and its salts; biguanide compounds such as chlorhexidine and the like Salts; amphoteric surfactants having an alkyl side chain such as alkyldiaminoethylglycine and alkylpolyaminoethylglycine; nonionic fungicides such as triclosan, glutaraldehyde and polyhexamethylene guanide; 4,5-dichloro-2 -Isothiazoline compounds such as octyl-4-isothiazolin-3-one and 2-octyl-4-isothiazolin-3-one; Imidazole compounds such as methyl 2-benzimidazole carbamate and 2- (4-thiazolyl) -benzimidazole Organic iodine compounds such as 3-iodo-2-propynyl-butyl-carbamate, diiodomethyl-p-to
  • insect repellent components include, for example, pyrethrin, cinerine, jasmolin, enpentrin, allethrin, phenothrin, teraretrin, praretrin, phthalthrin, resmethrin, framethrin, phenothrin, permethrin, cypermethrin, ciphenothrin, brathrin, etofenprox, Pyrethroid insecticides such as cyfluthrin, tefluthrin, bifenthrin, fenvalerate, imiprosulin, transfluthrin, fenpropatoline, fenfluthrin, paradichlorobenzene, naphthalene, camphor, diet, herb extract, horseradish extract, chili extract, perilla extract And tea extract.
  • odor components include fragrance components and malodorous components.
  • fragrance component examples include, for example, musk, ghost cat incense, Ryunobu incense, Abies oil, acjon oil, almond oil, angelica root oil, pagele oil, bergamot oil, perch oil, bore bellows oil, kayabuchi oil, gananga oil, Capsicum oil, caraway oil, cardamom oil, cassia oil, celery oil, cinnamon oil, citronella oil, cognac oil, coriander oil, cumin oil, camphor oil, jill oil, estgolan oil, eucalyptus oil, fennel oil, garlic oil, ginger Natural fragrances such as oil, grapefruit oil, hop oil, lemon oil, lemongrass oil, nutmeg oil, mandarin oil, mint oil, orange oil, sage oil, star anise oil, turpentine oil, resin; linalool, geraniol, nerol, citronellol , Hydroxycitronellol, menthol, borne
  • malodorous substances include, for example, nonanoic acid (eg, pelargonic acid), lactic acid, acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, iso-valeric acid, caproic acid, caprylic acid, caprin Carboxylic acids such as acid, myoleic acid, acrylic acid, methacrylic acid; ammonia, methylamine, ethylamine, n-propylamine, n-butylamine, n-allylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, ethylenediamine, pyridine, indole Nitrogen compounds such as skatole; ethers such as ethyl ether and iso-propyl ether; methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, iso-propyl mercaptan
  • components to be stabilized include colorants or dyes; active pharmaceutical ingredients; polyphenols; flavonoids; alkaloids; acids; physiologically functional substances such as vitamins.
  • colorants or dyes are as described in (1.3) (h) below.
  • active ingredients of pharmaceuticals include, for example, corticoids, androgens, estrogens, progestogens, proton pump inhibitors, 5-HT1 antagonists, sympathomimetic drugs, sympathomimetic drugs, anticholinergic drugs, tranquilizers, anxiolytic drugs , Antidote, analgesic, calcium antagonist, antiemetic, pituitary or hypothalamic hormone, antiparkinsonian, antihistamine, angiotensin II antagonist, lidocaine, nitroglycerin, neuroquinone antagonist, nonsteroidal antirheumatic drug, steroid Cardiac glycosides, anticoagulants, benzodiazepine derivatives, benzimidazole derivatives, piperidine derivatives, piperazine derivatives, imidazole derivatives, triazole derivatives, organic nitrates, prostaglandins, oligonucleotide antisense Drugs, acetylsalicylic acid, diclofenac sodium,
  • polyphenols examples include catechin, tannin, oolong tea polyphenol, chlorogenic acid, cacao mass polyphenol, and the like.
  • flavonoids include anthocyanin, hesperidin, neohesperidin, rutin, naringin, quercetin, isoflavone and naringenin.
  • alkaloids include capsaicin.
  • the acid examples include acetic acid, citric acid, malic acid, lactic acid, fumaric acid, tartaric acid, adipic acid and the like.
  • vitamins include vitamin A, vitamin B 1 , vitamin B 2 , vitamin B 6 , vitamin C, vitamin D, vitamin E, nicotinic acid, nicotinic acid amide, pantothenic acid and the like.
  • sustained-release components include, for example, ethanol, bactericides, antibacterial agents, insect repellent components, fungicide components, odor components, deodorant components, cosmetic components, physiologically functional substances (for example, active pharmaceutical ingredients; polyphenols) Flavonoids; alkaloids; acids; vitamins).
  • active pharmaceutical ingredients for example, active pharmaceutical ingredients; polyphenols
  • fungicide components for example, antibacterial agents, insect repellent components, fungicide components, odor components, deodorant components, cosmetic components, physiologically functional substances (for example, active pharmaceutical ingredients; polyphenols) Flavonoids; alkaloids; acids; vitamins).
  • disinfectant and antibacterial agent are as described in (a) of (1.3) above.
  • insect repellent component are as described in (b) of (1.3) above.
  • fungicide component are as described in (j) of (1.3) below.
  • odor component are as described in (c) of (1.3) above.
  • deodorant component are as described in (i) below (1.3).
  • cosmetic ingredients are as described in (1.3)
  • ultraviolet absorbers include, for example, nonylphenol; cinnamic acid, cinnamic acid derivatives (eg, octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2, 4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, 2-ethylhexyl p-methoxycinnamate (para Octyl methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate (sinoxate), cyclohexyl-p-methoxycinnamate, ethyl- ⁇ -cyano- ⁇
  • cosmetic ingredients include, for example, moisturizing ingredients, whitening ingredients, anti-inflammatory agents, cell activators and antioxidants.
  • moisturizing ingredients include, for example, chondroitin sulfate, hyaluronic acid, adenosine, glycerin, butylene glycol, hexylene glycol, 1,3-butylene glycol, propylene glycol, 1,2-hexanediol, 1,2- Pentanediol, hexanetriol, dipropylene glycol, 3-methyl-1,3-butanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, trimethylolpropane, pentaerythritol, hexylene glycol, Diglycerin, polyglycerin, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polyols such as ethylene glycol / propylene glycol copolymer and their heavy Organic acids (eg, citric acid, tartaric acid and lactic acid); glycol alkyl
  • whitening ingredients include arbutin, ⁇ -arbutin, tranexamic acid, ellagic acid, ascorbic acid, sodium ascorbate, magnesium ascorbate phosphate, disodium ascorbate phosphate, glucoside ascorbate, ascorbyl monostearate , Ascorbyl monopalmitate, ascorbyl dipalmitate, ascorbyl tetrahexyldecanoate, disodium ascorbate sulfate, sulfur, kojic acid, linoleic acid, linolenic acid, lactic acid, lucinol, chamomile extract, placenta extract, oil-soluble licorice extract , Mulberry extract, peony extract, toki extract, bitumen extract, horse chestnut bark extract, ibukitoranoekkisu and the like.
  • anti-inflammatory agent examples include ⁇ -aminocaproic acid, allantoin, lysozyme chloride, guaiazulene, glycyrrhizic acid and its salt, ⁇ -glycyrrhetinic acid, hydrocortisone and the like.
  • cell activators include, for example, deoxyribonucleic acid and salts thereof, adenylic acid derivatives such as adenosine triphosphate and adenosine monophosphate and salts thereof, ribonucleic acid and salts thereof, cyclic AMP, cyclic GMP, Nucleic acid-related substances such as flavin adenine nucleotides, guanine, adenine, cytosine, thymine, xanthine, caffeine, theopherin and their salts; egg components such as calf blood extract, serum deproteinized extract, spleen extract, avian, Chicken crown extract, shell extract, shellfish extract, royal jelly, silk protein and its degradation product or derivatives thereof, hemoglobin or its degradation product, lactoferrin or its degradation product, mollusc extract such as squid, fish meat extract, etc.
  • adenylic acid derivatives such as adenosine triphosphate and adenosine monophosphate
  • Extracts from mammals, birds, shellfish, insects, fish, molluscs, crustaceans, etc. Extracts; extracts from microorganisms such as fermented metabolites such as yeast extract, lactic acid bacteria extract, bifidobacteria extract; retinol and derivatives thereof (retinol palmitate, retinol acetate, etc.), retinal and derivatives thereof, dehydroretinal, Carotenoids such as tretinoin and carotene, thiamines (thiamine hydrochloride and thiamine sulfate), riboflavins (riboflavin, riboflavin acetate, etc.), pyridoxines (pyridoxine hydrochloride, pyridoxine dioctanoate, etc.), flavin adenine nucleotides, cyanocobalamin, Vitamins such as folic acids, nicotinic acids (nicotinamide, benzyl nicotinate
  • CHEN eg, Sandscon (Sophora subprostral CHUN et T. CHEN roots)
  • chestnuts mulberries
  • mulberries eg, mug (Morus alba L.)
  • other congeneric plants eg, roots of Sowakuhaku (magwa or other congenital plants) Skin
  • cake walnut eg Millettia reticulata, Mucuna birdwoodiana, etc.
  • Koganebana Sellaria baicalenis georgo, zoma, coffee, strawberry Jateorhiza columba root
  • Sato Millet hawthorn, sasanqua, salamander, saffron, sakura, pomegranate, zion, peonies, shobu, shirayuri, horsetail, watermelon, stevia, plum, licorice, pear, achillea millefolium, horseradish, horseradish, budgerigar, sesam
  • Yokuinin seed excluding barley seed coat
  • hermanus e.g., Rosa rugosa flower
  • rose genus plants e.g. Rose fruit
  • halibut peanuts, hikikoshi, hoshi, pistachio, hiba, sandalwood, loquat, dandelion, cypress, fujibaka, grape (for example, grape seeds), beech, blueberry, fludemanita, bowfish, physalis, physalis , Bokeh and related species (eg, bokeh and wobbly (eg, mokka (bokeh or berries)), hop, maikai, genus plant (eg, Ephedra distachya), cinnamon (E.
  • hermanus e.g., Rosa rugosa flower
  • rose genus plants e.g. Rose fruit
  • halibut peanuts
  • hikikoshi hoshi
  • pistachio hiba
  • sandalwood loqua
  • E.I. intermedia E.I. equisetina (e.g. mao (E. sinica, E. intermedia, E. equisetina rhizome))
  • mango shimasaicho, misohagi, honeybee, mimosa, murasakikinafuji and related species (e.g.
  • swordfish eg, Yakumoso (whole swordfish)
  • merirot melon, magnolia, peach, morohaya, oyster (Alpinia oxyphylla) (eg, Alpinia oxyphylla fruit), cornflower , Yachabushi, Mistletoe, Yanagita, Pokeweed, Prunus, Yukinoshita, Yuzuriha, Mugwort, Yorigusa (for example, juniper (Yorigusa root)), Rye, Lacanka (for example, Momo dicee grosvenori Swingle fruit), orchid, longan, mung bean (eg mung bean sprout), apple, lettuce, lemon, forsythia (Forsythia suisisa vaid) and its related species (eg Forsyridia sharp) Forsythia or Forsythia viridisima Lindley fruit)), rosemary, seaweed, soy (eg, bean or soy bean sprout), tea,
  • antioxidants include, for example, tocopherol, nordihydroguaiaretic acid, butylhydroxyanisole, dibutylhydroxytoluene, propyl gallate, octyl gallate, sodium bisulfite, erythorbic acid, sodium erythorbate, thiodipropionic acid
  • antioxidants include dilauryl, tolyl biguanide, p-hydroxyanisole, ascorbyl palmitate, ascorbyl stearate and the like.
  • colorants or dyes include, for example, gardenia pigments, safflower pigments, turmeric pigments, Benikouji pigments, carotene, anato pigments, paprika pigments, Dunaliella pigments, palm oil pigments, rosewood pigments, beet red, cochineal pigments, Lac pigment, perilla pigment, red cabbage pigment, red radish pigment, purple potato pigment, purple corn pigment, grape skin pigment, grape juice pigment, blueberry pigment, elderberry pigment, chlorophyll, spirulina pigment, cacao pigment, tamarind pigment, oyster pigment Edible natural pigments such as yellow pigment, charcoal pigment, charcoal pigment, boysenberry pigment, hibiscus pigment and onion pigment; yellow 4, yellow 5, red 2, red 3, red 40, red 102, Red 104, Red 105, Red 10 Edible synthetic pigments such as No.
  • deodorizing ingredients include plant-derived extracts such as horseradish, mustard, forsythia, holly mushrooms, thorns, hornets, camellias, lilacs, oysters, Japanese oaks, porcupines, ferns, white birch, tea, etc .; mushrooms, etc.
  • Extracts from mushrooms organic acids such as citric acid, malic acid, adipic acid, fumaric acid, lactic acid, gluconic acid, maleic acid and succinic acid; green tea flavonoids, lauryl methacrylate, geranyl crotonate, acetophenone myristate, paramethylacetophenone Benzaldehyde, benzyl acetate, benzyl propionate, amylcinnamic aldehyde, anisic aldehyde, diphenyl oxide, methyl benzoate, ethyl benzoate, methyl phenylacetate, ethyl phenylacetate, neoline, safrole, seda Oil, cedar vegetable oil, citronella oil, lavanten oil, petite grain oil, lemongrass oil, 3,4-hexanedione, 2,3-heptanedione, 5-methyl-2,3-hexanedione, 2,3-p
  • Examples of the fungicide component include, for example, thymol, hinokitiol, d-limonene, thiabendazole, methyl benzoimidazolylcarbamate, ⁇ -bromocinnamic aldehyde, parachlorometaxylenol, orthophenylphenol, N- (fluorodichloromethylthio) ) -Phthalimide, N-dichlorofluoromethylthio-N ′, N′-dimethyl-N-phenylsulfamide; 3-iodo-2-propynylbutyl carbamate, 3-bromo-2,3-diiodo-2-propenylethylcarbohydrate And organic iodine compounds such as nato, 2,3,3-triiodoallyl alcohol, iodopropargyl alcohol, 3-iodopropargyl-4-chlorophenyloxymethyl ether, and diiio
  • an alkaline aqueous solution of amylose is prepared.
  • the amount of amylose in the alkaline solution is preferably about 1% by weight or more, more preferably about 5% by weight or more, further preferably about 10% by weight or more, and most preferably about 15% by weight or more. is there.
  • the amount of amylose in the alkaline solution is preferably about 60% by weight or less, more preferably about 50% by weight or less, further preferably about 40% by weight or less, and further preferably about 30% by weight or less. More preferably about 25% by weight or less, most preferably about 20% by weight or less. If the amylose concentration is too low, the amount of water added to the viscose increases and the spinnability may deteriorate. If the amylose concentration is too high, it may be difficult to uniformly mix amylose in the viscose.
  • any alkali base used in the production of ordinary viscose can be used.
  • An alkali base is any substance that exhibits alkalinity when dissolved in water.
  • Examples of the alkali base include sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, sodium carbonate and potassium carbonate.
  • the alkaline base is preferably sodium hydroxide or potassium hydroxide.
  • the alkali base in an aqueous solution, the alkali base exists in a state dissociated into ions, but in this specification, it is described that the alkali base exists in the aqueous solution including the state dissociated into ions. .
  • sodium hydroxide dissociates into hydroxide ions and sodium ions in an aqueous solution, but sodium hydroxide is present in this aqueous solution.
  • the alkali base can be used at an arbitrary concentration in an alkaline solution.
  • the concentration of the alkali base material is preferably from about 0.25 N to about 10 N, and more preferably from about 0.5 N to about 2 N. If the concentration of the alkali base is too low, amylose may not dissolve. If the concentration of the alkali base is too high, chemical changes such as browning of the amylose solution may occur.
  • An alkaline aqueous solution of amylose can be prepared by dispersing amylose powder in water, adding an alkali, and stirring.
  • Amylose has the property of being easily crystallized, and in the state of amylose powder, amylose molecules are strongly bonded. Therefore, if it is mixed with viscose in the state of amylose powder, amylose tends to be in a state in which it cannot sufficiently exert the clathrate action when it becomes a amylose-containing rayon. Therefore, in the present invention, it is important to sufficiently dissolve amylose in an aqueous alkaline solution in advance.
  • amylose powder By dissolving the amylose powder in an aqueous alkaline solution, the bonds between the amylose molecules are loosened, the amylose molecules have a random structure, and when amylose-containing rayon is obtained, the amylose can fully exert its inclusion effect. Can be.
  • Viscose in the present invention, conventional viscose known in the art can be used. It is preferable that the concentration is appropriately adjusted in consideration of dilution by mixing with an aqueous amylose solution.
  • the alkaline aqueous solution of amylose and viscose can be mixed by any method known in the art.
  • the mixing method is not particularly limited.
  • an apparatus for adding and mixing an alkaline aqueous solution of amylose in viscose an injection-type or homomixer-type apparatus may be used.
  • the timing of addition and mixing may also be arbitrary. For example, even after defoaming viscose, it may be performed before defoaming and defoamed after addition and mixing.
  • the mixing ratio of the alkaline aqueous solution of amylose and viscose can be set appropriately.
  • the amount of amylose is preferably about 5% by weight or more, more preferably about 10% by weight or more. Preferably, it is more preferably about 15% by weight or more, and most preferably about 20% by weight or more.
  • the amount of amylose is preferably about 70% by weight or less, more preferably about 60% by weight or less. Preferably, it is about 50 wt% or less, more preferably about 40 wt% or less.
  • Increasing the amount of amylose with respect to the cellulose component is preferable because the inclusion effect increases, but if the amount of amylose is too large, filterability may deteriorate, spinnability may be adversely affected, and fiber strength may decrease. is there.
  • a viscose solution containing amylose can be spun by a conventionally known method to obtain an amylose-containing rayon tow. After spinning, it is in the form of a tow, but the functional rayon fiber can be obtained by cutting the tow in the form of a tow, or cutting the tow to an arbitrary fiber length, and then scouring by a conventionally known method.
  • the amylose-containing rayon tow may be cut during post-processing.
  • the resulting amylose-containing rayon fiber can be improved in the inclusion power of amylose by, for example, performing the heating step and the cooling step in a solvent after the fiber is produced.
  • solvents used are water, methanol, ethanol, propanol, butanol, isopropanol, acetone, acetonitrile, propionitrile, tetrahydrofuran, 1,4-dioxane, methyl isobutyl ketone, methyl ethyl ketone, ⁇ -butyl lactone, propylene carbonate , Sulfolane, nitromethane, N, N-dimethylformamide, N-methylacetamide, dimethylsulfoxide, dimethylsulfone, N-methylpyrrolidone, benzene, toluene, xylene, methylene chloride, chloroform, dichloroethane.
  • a solution in which an organic solvent is mixed with water is preferable.
  • organic solvents are methanol, ethanol, propanol, butanol, isopropanol, acetone, acetonitrile, propionitrile, tetrahydrofuran, 1,4-dioxane, methyl isobutyl ketone, methyl ethyl ketone, ⁇ -butyl lactone, propylene carbonate, sulfolane, nitromethane, N, N-dimethylformamide, N-methylacetamide, dimethyl sulfoxide, dimethyl sulfone, N-methylpyrrolidone, benzene, toluene, xylene, methylene chloride, chloroform, dichloroethane.
  • the amount of the organic solvent added to water may be about 0.5 parts by volume or more, about 1 part by volume or more, about 2 parts by volume or more, or about 4 parts by volume or more with respect to 10 parts by volume of water.
  • the addition amount of the organic solvent can be added up to the upper limit of the solubility of the organic solvent in water.
  • the amount of the organic solvent added to the water is, for example, about 100 parts by volume or less, about 95 parts by volume or less, about 90 parts by volume or less, about 80 parts by volume or less, about 60 parts by volume or less, about 40 parts by volume or less.
  • the volume may be less than or equal to about 20 parts by volume.
  • the heating temperature and heating time are not particularly limited.
  • the heating temperature can be, for example, about 80 ° C or higher, about 90 ° C or higher, about 100 ° C or higher, about 110 ° C or higher, about 120 ° C or higher, or about 130 ° C or higher.
  • the heating temperature can be any temperature as long as there is no particularly harmful effect except that the state of amylose changes.
  • the heating temperature may be, for example, about 200 ° C. or lower, about 180 ° C. or lower, about 160 ° C. or lower, about 140 ° C. or lower.
  • the heating time is, for example, about 5 minutes or more, about 10 minutes or more, about 20 minutes or more, about 30 minutes or more, about 40 minutes or more, about 50 minutes or more, about 60 minutes (1 hour) or more, about 2 hours or more, It may be about 3 hours or more, about 4 hours or more, about 5 hours or more, about 6 hours or more, about 8 hours or more, about 12 hours or more, about 24 hours or more, and the like.
  • the heating time is, for example, about 1 month or less, about 1 week or less, about 3 days or less, about 2 days or less, about 1 day (24 hours) or less, about 18 hours or less, about 16 hours or less, about 14 hours or less, About 12 hours or less, about 10 hours or less, about 8 hours or less, about 6 hours or less, about 5 hours or less, about 4 hours or less, about 3 hours or less, about 2 hours or less, about 1 hour or less, about 30 minutes or less, It may be about 20 minutes or less, about 10 minutes or less, and the like.
  • the amylose-containing rayon is cooled to a predetermined temperature (for example, room temperature).
  • This predetermined temperature can be, for example, about 10 ° C. or higher, about 15 ° C. or higher, about 20 ° C. or higher, about 25 ° C. or higher, and the like.
  • This predetermined temperature may be, for example, about 30 ° C. or lower, about 25 ° C. or lower, about 20 ° C. or lower.
  • the cooling from the heating temperature to the predetermined temperature may be performed by cooling. That is, the time required for cooling differs depending on the ambient temperature of the amylose-containing rayon. In another specific embodiment, it is preferred that the cooling from the heating temperature to the predetermined temperature is as short as possible.
  • the time required for cooling can be, for example, about 10 seconds or more, about 20 seconds or more, about 30 seconds or more, about 1 minute or more, about 5 minutes or more, and the like. In embodiments where it is preferred to cool in a short time, the time required for cooling can be, for example, about 5 hours or less, about 4 hours or less, about 3 hours or less, about 2 hours or less, about 1 hour or less, and the like.
  • the heating step and the cooling step may be performed after spinning of the amylose-containing rayon and before drying, or may be performed after drying after spinning. After this heating and cooling treatment, the amylose-containing rayon fiber can be dried according to a conventional method, if necessary.
  • amylose-containing rayon fiber can be improved in the inclusion power of amylose by, for example, neutralization after treatment with alkali.
  • the alkali base that can be used for the alkali treatment can be any alkali base.
  • the alkali base include sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate and calcium carbonate.
  • the alkaline base is preferably sodium hydroxide, potassium hydroxide, sodium phosphate or sodium carbonate.
  • the alkali base may also be a mixture of these alkalis.
  • the acid that can be used for the neutralization treatment can be any acid.
  • acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, bicarbonate, perchloric acid; and acetic acid, propionic acid, lactic acid, maleic acid, fumaric acid, tartaric acid, malic acid, citric acid And organic acids such as ascorbic acid. Also, a mixture of these acids may be used.
  • the alkali treatment and the acid treatment are preferably performed by immersing the amylose-containing rayon in a bath of an aqueous alkali solution or an aqueous acid solution, but in some cases, the treatment may be performed by any other method such as spraying or stamping.
  • the concentration of the alkaline aqueous solution varies depending on the type and concentration of the alkali base.
  • the concentration of the alkaline aqueous solution is preferably about 1 ⁇ 10 ⁇ 5 N or more, more preferably about 1 ⁇ 10 ⁇ 4 N or more, more preferably about 1 ⁇ 10 ⁇ 3 N or more, more preferably It is about 1 ⁇ 10 ⁇ 2 or more, more preferably about 1 ⁇ 10 ⁇ 1 or more.
  • the concentration of the alkaline aqueous solution is preferably about 20 N or less, more preferably about 10 N or less, more preferably about 5 N or less, and further preferably about 1 N or less.
  • the concentration of the acid aqueous solution varies depending on the type and concentration of the acid.
  • the concentration of the aqueous acid solution is preferably about 1 ⁇ 10 ⁇ 5 normal or higher, more preferably about 1 ⁇ 10 ⁇ 4 normal or higher, more preferably about 1 ⁇ 10 ⁇ 3 normal or higher, more preferably It is about 1 ⁇ 10 ⁇ 2 or more, more preferably about 1 ⁇ 10 ⁇ 1 or more.
  • the concentration of the aqueous acid solution is preferably about 20 N or less, more preferably about 10 N or less, more preferably about 5 N or less, and further preferably about 1 N or less.
  • the temperature of the aqueous alkali solution or the aqueous acid solution during the alkali treatment and the acid treatment is not particularly limited.
  • the temperature of the aqueous alkali solution or aqueous acid solution is, for example, about 120 ° C. or less, about 110 ° C. or less, about 100 ° C. or less, about 90 ° C. or less, about 80 ° C. or less, about 70 ° C. or less, about 60 ° C. or less, about 50 ° C. or less.
  • the temperature of the alkaline aqueous solution or the acid aqueous solution is, for example, about 0 ° C. or higher, about 5 ° C. or higher, about 10 ° C.
  • the heating time for alkali treatment and acid treatment is, for example, about 10 minutes or more, about 20 minutes or more, about 30 minutes or more, about 40 minutes or more, about 50 minutes or more, about 60 minutes (1 hour) or more, about 2
  • the time may be about 3 hours or more, about 4 hours or more, about 5 hours or more, about 6 hours or more, about 8 hours or more, about 12 hours or more, about 24 hours or more.
  • the heating time for alkali treatment and acid treatment is, for example, about 1 month or less, about 1 week or less, about 3 days or less, about 2 days or less, about 1 day (24 hours) or less, about 18 hours or less, about 16 hours or less.
  • the alkali treatment may be performed after spinning of the amylose-containing rayon and before drying, or after spinning and after drying. After this alkali treatment, the amylose-containing rayon fiber can be dried according to a conventional method, if necessary.
  • amylose-containing rayon fiber In the amylose-containing rayon fiber of the present invention, amylose is dispersed and retained in the rayon fiber. Here, it is considered that amylose is dispersed and retained almost uniformly in the rayon fiber.
  • the amount of amylose dispersed and retained in the rayon fiber can be arbitrarily set by changing the mixing ratio of cellulose and amylose in the viscose in the production of the amylose-containing rayon fiber.
  • the amount of amylose dispersed and retained in the rayon fiber is preferably about 1% by weight or more, more preferably about 5%, when the total amount of cellulose and amylose in the rayon fiber is 100% by weight. % By weight or more, more preferably about 10% by weight or more.
  • the amount of amylose dispersed and retained in the rayon fiber is preferably about 60% by weight or less, more preferably about 50%, when the total amount of cellulose and amylose in the rayon fiber is 100% by weight.
  • % By weight or less, more preferably about 40% by weight or less, more preferably about 30% by weight or less, and still more preferably about 20% by weight or less. If the amount of amylose dispersed and retained in the rayon fiber is too small, the desired effect may not be obtained sufficiently. If the amount of amylose dispersed and retained in the rayon fiber is too large, the viscosity of the viscose will increase, making it difficult to stably produce the rayon fiber, and decreasing the physical properties such as the strength and elongation of the rayon fiber. There is a case to do.
  • the amylose-containing rayon fiber is preferably subjected to at least one of heating and cooling treatment as described in (2.5) and alkali treatment as described in (2.6). This is because the inclusion power of amylose can be improved by performing a heating / cooling treatment or an alkali treatment.
  • the amylose-containing rayon of the present invention does not contain a quaternary ammonium salt compound and has not been treated with a quaternary ammonium salt compound.
  • the amylose-containing rayon of the present invention is in either a state where no guest substance is included or a state where a guest substance is included.
  • the amylose-containing rayon that does not include the guest substance comes into contact with a substance that can be included by amylose, the substance is included.
  • the amylose-containing rayon in the state of inclusion of the guest substance can release the guest substance by a change in heat, moisture, etc., as in the case of a normal inclusion compound.
  • amylose is not substantially eluted by washing.
  • the term “substantially does not elute amylose by washing” means that the amount of amylose eluted by washing is 10% by weight or less of the amylose contained in the amylose-containing rayon fiber. It means that there is.
  • the ease of elution of amylose from the amylose-containing rayon fiber is preferably determined under the following conditions: 40 times the amount of the amylose-containing rayon fiber as a washing liquid (0.75 mg / mL aqueous detergent solution.
  • Lion Corporation top (24% surfactant (sodium alphasulfo fatty acid ester, sodium fatty acid, polyoxyethylene alkyl ether), alkaline agent (carbonate), dissolution promoter, enzyme, fluorescent whitening agent, bleaching as other components
  • surfactant sodium alphasulfo fatty acid ester, sodium fatty acid, polyoxyethylene alkyl ether
  • alkaline agent carbonate
  • dissolution promoter enzyme
  • fluorescent whitening agent bleaching as other components
  • the elution amount of amylose under these conditions is preferably about 10% by weight or less of the amylose contained in the amylose-containing rayon fiber, more preferably about 8% by weight or less, and about 5% by weight or less. Still more preferably, it is particularly preferably not more than about 3% by weight, most preferably not more than about 1% by weight. About 0.5 wt% or less, about 0.4 wt% or less, about 0.3 wt% or less, about 0.2 wt% or less, about 0.1 wt% or less, about 0.05 wt% or less, about 0 It is also very preferable that the content is 0.01% by weight or less.
  • the term “has the ability to clathrate a guest substance” means that amylose is able to clathrate the guest substance.
  • Inclusion includes not only intramolecular inclusion but also intermolecular inclusion.
  • Intramolecular inclusion refers to a phenomenon in which a guest substance is included in one molecule of amylose.
  • Intermolecular inclusion refers to a phenomenon in which a guest substance is included between a plurality of amylose molecules or between amylose molecules and cellulose molecules.
  • Natural and synthetic amylose has three crystal forms called A-type, B-type and V-type.
  • the crystal form differs depending on the type of plant, extraction solvent, precipitant and the like when extracted and purified from natural starch.
  • Type A amylose is obtained from cereal starches such as wheat and corn.
  • B-type amylose is obtained from potato starches such as potato and sweet potato. Both A-type amylose and B-type amylose have a structure in which ⁇ -1,4-glucan chains take a double helix in parallel.
  • type V amylose is obtained by adding a precipitating agent such as ethanol or butanol to natural starch.
  • V-type amylose has a structure in which the ⁇ -1,4-glucan chain takes a single helix.
  • V-type amylose In the case of amylose in a powder state, in the case of A-type amylose and B-type amylose, V-type amylose has intramolecular inclusion force.
  • A-type amylose and B-type amylose are considered to have intermolecular inclusion force, and V-type amylose is considered to have both intramolecular inclusion force and intermolecular inclusion force.
  • Amorphous amylose can also show inclusion power. It is considered that such amylose takes a specific structure in the presence of a guest substance and changes into a state in which an inclusion action can be exerted.
  • the crystal form of amylose can be determined by methods known in the art. For example, it can be determined using X-ray diffraction according to the description in WO 2006/082968 pamphlet. Conveniently, it is possible to determine whether amylose is in a state where it can exert an inclusion action by testing whether amylose includes nonylphenol. Amylose in a state where it can exert an inclusion action is also called functional amylose.
  • the amylose-containing rayon fiber is impregnated with nonylphenol by immersing 50 mg of the amylose-containing rayon fiber in 3 mL of 50% aqueous methanol solution containing nonylphenol having a concentration of 100 ppm at 25 ° C. for 3 hours.
  • This amylose-containing rayon fiber is packed in a column and washed twice with 5 mL of a 10% aqueous methanol solution.
  • the clathrated nonylphenol is eluted twice with 5 mL of methanol, and the eluate is collected together.
  • the amount of nonylphenol in the eluate is quantified by HPLC to determine the amount of nonylphenol encapsulated.
  • the inclusion force of amylose-containing rayon is defined by the following formula.
  • liquid chromatography conditions are as follows: TSKgel ODS-100Z (manufactured by TOSOH) is used as a column, UV detector SPD-6A (manufactured by Shimadzu Corporation) is used as a detector, and LC-6A (manufactured by Shimadzu Corporation) is used as a liquid feed pump.
  • the column is kept at 40 ° C. and analyzed using 80% methanol as eluent at a flow rate of 1.0 mL / min.
  • control rayon fiber which is the same as the amylose-containing rayon fiber, is eluted, except that it does not contain amylose. Therefore, when a control rayon fiber can be prepared, the inclusion force can be determined by the following method.
  • Each rayon fiber is impregnated with nonylphenol by immersing 50 mg of rayon fiber containing amylose and 50 mg of control rayon fiber not containing amylose in 3 mL of 50% aqueous methanol solution containing 100 ppm nonylphenol at 25 ° C. for 3 hours.
  • the concentration of nonylphenol in the aqueous solution before and after soaking the rayon fiber is measured by liquid chromatography.
  • the nonylphenol adsorption rate (%) is determined by the following formula from the decrease amount of nonylphenol before and after immersion.
  • the inclusion force of rayon containing amylose is defined by the following formula.
  • amylose can include nonylphenol but cannot adsorb it, the inclusion force of amylose can be calculated by this formula.
  • amylose-containing rayon fiber of the present invention can be used in various forms.
  • the amylose-containing rayon fiber of the present invention is used as a cotton fabric as it is, or as a yarn by itself or blended with other fibers, or as a fabric such as a knitted fabric or a nonwoven fabric (including a paper wet nonwoven fabric), It can be suitably used as curtains, bedding, shoji paper, wallpaper, hats, carpets, sofa skin materials, and other deodorizing goods.
  • the amylose-containing rayon fiber of the present invention can be used for various secondary processed products in the same manner as ordinary rayon fibers. Such secondary processed products include cotton, yarn, non-woven fabric, cloth, paper, and the like.
  • amylose-containing rayon fibers Methods for producing these secondary processed products from amylose-containing rayon fibers are known in the art. For example, in the case of producing paper from amylose-containing rayon fibers, amylose-containing rayon fibers cut into short fibers are mixed with ordinary paper raw materials, or the short amylose-containing rayon fibers are made alone to make paper. Paper can be made from the contained rayon fibers. Further, these secondary processed products can be used for products such as clothing, fabrics, filters, processed products for cosmetics, medical products, daily products, packaging products, sanitary products, and other sanitary materials. Fabric is a product that uses fabrics, fabrics, etc., and is often used in the interior industry in a slightly broad sense from the generic name of fabrics and fabrics. Curtains, tablecloths, chairs and sofa upholstery fabrics, cushions In general, cloth covers such as bed covers, including cloth wall coverings.
  • amylose-containing rayon fiber of the present invention The purpose of use of the amylose-containing rayon fiber of the present invention can be roughly classified into the following two. (1) a method of using the guest material as it is without being included, and (2) a method of using the guest material in a state of being included.
  • Deodorizing means collecting (containing) odor components. Examples of odor components that can be collected are as described in (1.3) (c). Specific product examples for the purpose of deodorization include pet sheets with a deodorizing function, clothing with a deodorizing function, sanitary products with a deodorizing function, bedding with a deodorizing function, a filter for an air purifier, wallpaper, and the like.
  • Concentration (recovery) purpose “Concentration” means that the concentration is increased by collecting the target material present in a diluted state.
  • the target substance to be concentrated may be any substance as long as it can be included in amylose. Examples of the target substance are as described in (1.3).
  • Specific product examples for the purpose of concentration include filters and columns for collecting these target substances (for example, filters and columns for collecting surfactants, filters and columns for collecting fatty acids, physiologically functional substances (for example, effective pharmaceutical products) Components; polyphenols; flavonoids; alkaloids; acids; vitamins) recovery filters and columns, alkyl compound recovery filters and columns, and the like.
  • Removal purpose means collecting and removing the contaminants mixed in the target substance or product.
  • the target substance and the contaminant substance to be removed may be any substance as long as it can be included in amylose. Examples of the target substance and the contaminant substance to be removed are as described in (1.3). Specific product examples for removal purposes include tar or nicotine removal filters, exhaust gas component (eg, pyrene compound) removal filters, water purification filters and columns, air purification filters, masks, cleaning products, personal cleaning products. Etc.
  • exhaust gas component eg, pyrene compound
  • Purification means that a specific substance is purified from a mixture to a pure substance.
  • the substance to be purified may be any substance as long as it can be included in amylose.
  • Examples of substances to be purified are as described in (1.3).
  • Specific examples of products for purification purposes include filters and columns for purification of these target substances (for example, filters and columns for purification of surfactants, filters and columns for purification of fatty acids, physiologically functional substances (for example, effective pharmaceutical products)
  • Ingredients Polyphenols; Flavonoids; Alkaloids; Acids; Vitamins
  • amylose-containing rayon fiber is directly put into a container containing the mixture, and the target substance.
  • amylose-containing rayon fibers are collected after adsorbing (inclusion) and the target substance is then eluted and collected.
  • Sterilization purpose or antibacterial purpose “Sterilization” refers to killing microorganisms. “Antimicrobial” refers to inhibiting or inhibiting the growth of microorganisms. Microorganism refers to a microscopic organism. Examples of microorganisms include bacteria, fungi (eg, yeast), protozoa, and viruses.
  • a product for sterilization or antibacterial purposes is a product whose purpose is to kill microorganisms or prevent them from growing on the product surface or inside the product.
  • examples of the guest substance to be included in the amylose-containing rayon fiber are as described in (a) of (1.3) above.
  • sterilization / antibacterial purposes include sanitary products (masks, gloves, apron, hats, pillow covers, seat head covers, wet tissues, towels, insoles, shoe deodorization, clothing covers, etc. ), Building materials in walls, wallpaper, gauze, bandages, rolling pins, bedding (pillow covers, sheets, duvet covers, pillows or cotton in duvets), interior supplies (curtains, shoji screens, sofa covers, doormats, cushions, etc.) And a kitchen or bath or toilet article (wet tissue, toilet seat cover, toilet mat, bathtub mat, kitchen mat, etc.).
  • Insect-proof or mold-proof purpose “Insect repellent” means keeping insects away and preventing insects from attaching. “Anti-fungus” is to prevent the growth of mold. Examples of guest substances to be included in amylose-containing rayon fibers for this purpose include insect repellents and fungicides. Examples of the insect repellent are as described in (b) of (1.3) above. Examples of the fungicide are as described in (j) of (1.3) above.
  • Specific examples of products include insect repellent sheets, insect repellent mats, insect repellent curtains, insect repellent clothing, fungicide repellent sheets, mold repellent mats, fungicidal curtains, and fungi repellent clothing.
  • (G) Fragrance purpose or deodorant purpose “Attaching” means adding a flavor component (fragrance) to perfume. “Deodorizing” is to remove the smell.
  • Examples of guest substances to be included in amylose-containing rayon fibers for perfume purposes are as described in (1.3) (c) above.
  • An example of a guest substance to be included in amylose-containing rayon fibers for the purpose of deodorization is a deodorizing agent.
  • Examples of the deodorizing agent are as described in (i) of (1.3) above.
  • fragrance and deodorization purposes include clothing, hygiene products (eg masks, gloves, apron, hats, pillow covers, seat head covers, wet tissues, towels, insoles) , Deodorizing shoes, clothing covers, etc.), building materials in walls, wallpaper, gauze, bandages, rolling pins, bedding (eg pillow covers, sheets, duvet covers, pillows or duvet cotton), interior goods (eg curtains) , Paper sliding doors, sofa covers, doormats, cotton in cushions, etc.), kitchen or bath or toilet articles (eg, wet tissue, toilet seat covers, toilet seat mats, bath mats, kitchen mats, etc.).
  • hygiene products eg masks, gloves, apron, hats, pillow covers, seat head covers, wet tissues, towels, insoles
  • building materials in walls wallpaper, gauze, bandages, rolling pins
  • bedding eg pillow covers, sheets, duvet covers, pillows or duvet cotton
  • interior goods eg curtains
  • Stabilization refers to preventing decomposition or modification of a substance that is unstable and decomposes or denatures alone. By including a substance that is unstable by itself, the substance can be stabilized and stored for a longer period of time than when it is alone.
  • guest substances that can be included in amylose-containing rayon fibers for this purpose include substances that are easily decomposed by light, ultraviolet rays, heat, oxygen, and the like and can be included in amylose.
  • Examples of such guest substances are as described in (d) of (1.3) above.
  • Specific examples of products include medical patches and fabric products that do not easily lose color.
  • Specific product examples include sanitary products (masks, gloves, apron, hats, pillowcases, seat head covers, wet tissues, towels, insoles, shoe deodorizers, clothing covers, etc.), inside walls Building materials, wallpaper, gauze, bandages, rolling pins, bedding (such as pillowcases, sheets, duvet covers, pillows or duvet cotton), interior supplies (curtains, shoji screens, sofa covers, doormats, cotton in cushions, etc.) Kitchen or bath or toilet articles (wet tissue, toilet seat cover, toilet seat mat, bathtub mat, kitchen mat, etc.), insect repellent sheets, insect repellent mats, insect repellent curtains, insect repellent clothes, anti-mold sheets, anti-mold mats, anti-mold curtains, anti-mold clothes, etc. Is mentioned.
  • UV protection purpose “Ultraviolet light prevention” is to reduce or eliminate the amount of ultraviolet light.
  • an ultraviolet absorbing substance also referred to as an ultraviolet absorbent
  • Examples of the ultraviolet absorbing material are as described in the above (1.3) (f).
  • Specific examples of products include hats with UV protection, clothing with UV protection, umbrellas with UV protection, gloves with UV protection, curtains with UV protection.
  • (K) Purpose of applying makeup function “Providing cosmetic functions” is expected to be normally applied in cosmetics, such as moisturizing action, whitening action, anti-inflammatory action, blood circulation promoting action, antioxidant action, antiperspirant action, cooling action, cell activating action, etc. Function.
  • Examples of guest substances to be included in amylose-containing rayon fibers for this purpose include moisturizing ingredients, whitening ingredients, anti-inflammatory agents, cell activators and antioxidants.
  • Examples of the moisturizing component, whitening component, anti-inflammatory agent, cell activator and antioxidant are as described in (g) of (1.3) above.
  • Specific examples of products include face masks, poultices, and bandages.
  • (L) Purpose of providing medical functions “Granting a medical function” means giving a medical purpose function.
  • guest substances to be included in amylose-containing rayon fibers for this purpose include active pharmaceutical ingredients and hair restorers.
  • Examples of the active ingredient of the pharmaceutical are as described in (d) of (1.3) above.
  • Specific examples of products include adhesive bandages, gauze, and clothing.
  • the term “chemical substance-containing solution” refers to a solution containing a chemical substance.
  • the chemical substance can be any chemical substance that is included by amylose.
  • the chemical substance may be any guest substance described in (1.3) above.
  • the chemical substance is neither iodine nor polyiodide ions.
  • iodine includes both iodine molecules and iodide ions.
  • iodine in the case of “iodine or polyiodide ion” means an iodine molecule.
  • the chemical substance-containing solution may be any solution as long as it contains a chemical substance.
  • the method of the present invention is a method of capturing a chemical in a fiber to concentrate, recover, remove or isolate the chemical, wherein the amylose-containing rayon fiber is contacted with the chemical. And including the chemical substance in amylose of the amylose-containing rayon fiber.
  • the chemical substance contained in the chemical substance-containing solution is brought into contact with the amylose-containing rayon fiber by bringing the chemical substance-containing solution into contact with the chemical substance-containing solution.
  • amylose Of amylose.
  • amylose-containing rayon fiber it is preferable to use an amylose-containing rayon fiber that does not include any guest substance.
  • Amylose rayon fibers can be used in any shape.
  • the amylose rayon fiber can be used in any shape such as a fiber shape, a filter shape, a column shape, and a cotton shape.
  • the contact between the amylose-containing rayon fiber and the chemical substance-containing solution can be performed by any method. For example, immerse the amylose-containing rayon fiber in the chemical substance-containing solution, spray the chemical substance-containing solution onto the amylose-containing rayon fiber, or process the amylose-containing rayon fiber into a column shape or filter shape, and add the chemical substance
  • the solution can be passed through.
  • the chemical substance when the chemical substance is a gaseous substance, the chemical substance can be included in amylose by bringing the amylose-containing rayon fiber into contact with the gaseous chemical substance.
  • the time and temperature at which the amylose-containing rayon fiber is brought into contact with the chemical substance can be arbitrarily set.
  • the temperature of the chemical substance-containing solution is, for example, about ⁇ 20 ° C. or higher, about 0 ° C. or higher, about 10 ° C. or higher, about 15 ° C. or higher, about 20 ° C. As described above, it may be about 25 ° C. or higher.
  • the temperature of the chemical substance-containing solution is, for example, about 120 ° C. or less, about 100 ° C. or less, about 90 ° C.
  • the immersion time is, for example, about 5 minutes or more, about 10 minutes or more, about 20 minutes or more, about 30 minutes or more, about 40 minutes or more, about 50 minutes or more, About 60 minutes (1 hour) or more, about 2 hours or more, about 3 hours or more, about 4 hours or more, about 5 hours or more, about 6 hours or more, about 8 hours or more, about 12 hours or more, about 24 hours or more possible.
  • the immersion time is, for example, about 1 month or less, about 1 week or less, about 3 days or less, about 2 days or less, about 1 day (24 hours) or less, about 18 hours or less, about 16 hours or less, about 14 hours or less, About 12 hours or less, about 10 hours or less, about 8 hours or less, about 6 hours or less, about 5 hours or less, about 4 hours or less, about 3 hours or less, about 2 hours or less, about 1 hour or less, about 30 minutes or less, It may be about 20 minutes or less, about 10 minutes or less, and the like.
  • the encapsulated chemical substance is eluted in water by, for example, immersing the amylose-containing rayon fiber encapsulating the chemical substance in water. By partially or completely evaporating the water, the chemical is concentrated or purified. When a solution containing a large number of substances other than the target chemical substance is used, the target chemical substance is specifically encapsulated in amylose-containing rayon fiber and then eluted and concentrated in water. Is specifically enriched.
  • Enhance the concentration of chemical substances is called “concentration of chemical substances”. For example, when a chemical substance is taken out from the chemical substance-containing solution and a solution containing a chemical substance having a higher concentration than the chemical substance-containing solution is obtained, it can be said that the chemical substance is concentrated.
  • the method of the present invention can be used to remove this chemical from the target.
  • the solution containing the target chemical substance contains a plurality of types of substances other than the target chemical substance and these substances are not included in amylose
  • the chemical substance-containing solution and the amylose-containing rayon fiber are brought into contact with each other. Only the target chemical is included in amylose. Therefore, the method of the present invention can be used to isolate this chemical.
  • the guest substance can be included in the amylose-containing rayon fiber.
  • the contact method include a method in which the amylose-containing rayon fiber is immersed in a solution containing a guest substance in a liquid phase; a solution containing the guest substance is sprayed on the amylose-containing rayon fiber, and a guest compound vapor is contacted. There is a method of contacting in the gas phase.
  • the guest substance is a substance that can be dissolved in an aqueous solution at about 130 ° C.
  • thermostable glucan phosphorylase derived from potato tuber prepared and purified according to the method described in Example 2-1A of WO 2004/113525 pamphlet (having the amino acid sequence of SEQ ID NO: 34 of WO 2004/113525 pamphlet) 1 unit / ml) and a heat-resistant Streptococcus mutans-derived sucrose phosphorylase prepared according to the method described in Example 2A of WO 2005/24008 (amino acid of SEQ ID NO: 22 of WO 2005/24008) Arrangement 1 unit / ml) was added and incubated at 37 ° C.
  • amylose having a polymerization degree of 32 to 4818 (Mw 5.2 to 780.5 kDa) was obtained by changing the concentration ratio between sucrose and the primer (that is, maltooligosaccharide mixture).
  • the dispersity (Mw / Mn) of amylose in these samples was 1.2 or less.
  • the glucan synthesized in Synthesis Example 1 was completely dissolved with 1N sodium hydroxide and neutralized with an appropriate amount of hydrochloric acid, and then about 300 ⁇ g of glucan was subjected to gel filtration chromatography using a differential refractometer and a multi-angle light scattering detector in combination. The average molecular weight was determined by means of a graph.
  • Shodex SB806M-HQ manufactured by Showa Denko
  • DAWN-DSP multi-angle light scattering detector
  • a differential refractometer Shodex RI-71, manufactured by Showa Denko
  • the column was kept at 40 ° C., and 0.1 M sodium nitrate solution was used as an eluent at a flow rate of 1 mL / min.
  • the obtained signals were collected using data analysis software (trade name ASTRA, manufactured by Wyatt Technology), and analyzed using the same software to determine the weight average molecular weight.
  • Viscose was prepared from raw pulp (LDPT: Nippon Paper Chemicals) according to a conventional method. This viscose had a cellulose content of 9% by weight, an alkali content of 5% by weight and a falling ball viscosity of 60 seconds.
  • Each of the enzyme-synthesized amyloses (without branch structure) having an average molecular weight of 5.2 ⁇ 10 3 , 4.62 ⁇ 10 4 or 1.174 ⁇ 10 5 synthesized in Synthesis Example 1 was dissolved in 5 wt% NaOH aqueous solution. Then, an alkaline aqueous solution of amylose was prepared. Any one of these aqueous solutions and viscose were mixed according to a conventional method and then spun to obtain an amylose-containing rayon fiber. A control rayon fiber was obtained by spinning only with viscose without mixing with an alkaline aqueous solution (Comparative Example 1-1). By changing the mixing ratio of the alkaline aqueous solution and viscose, the amount ratio (weight ratio) of amylose and cellulose was changed as shown in Table 2 below.
  • amylose having an average molecular weight of 2.810 ⁇ 10 5 or 7.805 ⁇ 10 5 synthesized in Synthesis Example 1 was used, it was difficult to uniformly dissolve even at an amylose concentration of 5%. Even if it can be dissolved, the viscosity of the obtained amylose alkaline solution is high, and it was difficult to uniformly mix with the viscose solution. The fiber could not be synthesized.
  • amylose having an average molecular weight of 2.810 ⁇ 10 5 which is an enzyme-synthesized amylose having a molecular weight of 500,000 or less, is characteristic of enzyme-synthesized amylose. there were.
  • amylose content in the amylose-containing rayon fiber and the control rayon fiber was quantified by the following method. 20 mg of amylose-containing rayon fiber or control rayon fiber was dissolved in a copper ammonia solution, and then neutralized with an acetic acid solution at the same time as neutralization (total 2 mL) to reprecipitate only cellulose. The mixture was centrifuged at 13,200 ⁇ g for 10 minutes, and the amount of amylose in the supernatant was quantified by the phenol sulfate method. The results are shown in Table 2.
  • amylose having an average molecular weight of 5.2 ⁇ 10 3 in the rayon was extremely small. From these facts, amylose having an average molecular weight of 5.2 ⁇ 10 3 does not remain in the rayon, while amylose having a molecular weight of 4.62 ⁇ 10 4 or more can be contained inside the rayon. It became clear.
  • Example 2 Evaluation of inclusion force of amylose-containing rayon fiber> The inclusion force of the amylose-containing rayon fibers produced in Examples 1-1 to 1-4 and Comparative Examples 1-2 to 1-3 and the control rayon fiber produced in Comparative Example 1-1 was measured using nonylphenol as a guest substance. It was measured.
  • TSKgel ODS-100Z (manufactured by TOSOH) was used as the column, UV detector SPD-6A (manufactured by Shimadzu Corporation) was used as the detector, and LC-6A (manufactured by Shimadzu Corporation) was used as the liquid feed pump.
  • the column was kept at 40 ° C. and 80% methanol was used as eluent at a flow rate of 1.0 mL / min.
  • the inclusion force (%) of the amylose-containing rayon fiber was calculated based on the above equation (3). That is, calculation was performed by subtracting the nonylphenol adsorption rate of the control rayon fiber from the nonylphenol adsorption rate of the amylose-containing rayon fiber. The results are shown in Table 3.
  • the adsorption rate of nonylphenol of the amylose-containing rayon fibers having an average molecular weight of 5.2 ⁇ 10 3 in Comparative Examples 1-2 and 1-3 is almost the same as that of the control rayon in Comparative Example 1-1, and the inclusion force is 1. It was found that amylose-containing rayon fibers having a low molecular weight of 3% or less and an average molecular weight of 5.2 ⁇ 10 3 have almost no inclusion force. In contrast, the amylose-containing rayon of Examples 1-1 to 1-4 showed an adsorption rate of 1.8 times to 4.3 times that of Comparative Example 1-1, and was 4.1% to 16.7%. It was found to have a high inclusion force. This inclusion force increased as the amylose content increased and the molecular weight of amylose increased.
  • amylose having an average molecular weight of 2.810 ⁇ 10 5 or more could not be contained in rayon fiber, in order to produce rayon fiber containing amylose in a state capable of exerting inclusion force against nonylphenol, the average of amylose It became clear that the molecular weight should be greater than 5.2 ⁇ 10 3 and less than 2.810 ⁇ 10 5 .
  • Example 3 Washing test of amylose-containing rayon fiber> The amylose-containing rayon fibers produced in Examples 1-2, 1-4 and Comparative Example 1-3 or the control rayon fiber produced in Comparative Example 1-1 were subjected to a washing test, and the stability of amylose in the amylose-containing rayon fibers was determined. The sex was confirmed.
  • each rayon fiber was placed in water or a commercially available enzyme-containing detergent (lion top) solution adjusted to 0.75 mg / mL for 3 hours.
  • the solution was transferred to a 2 mL centrifugal filter (5 ⁇ m) and centrifuged at 12,000 ⁇ g for 4 minutes to recover the solution.
  • the following operation was performed.
  • the filtrate of the rayon fiber washed with water was diluted 3 times with water, and glucoamylase (18 U / mL) and ⁇ -amylase (2.6 U / mL) were allowed to act.
  • the filtrate of rayon washed with detergent was neutralized by diluting 3 times with a 1% aqueous acetic acid solution, and then reacted with glucoamylase (18 U / mL) and ⁇ -amylase (2.6 U / mL).
  • Amylose was converted to glucose by the action of glucoamylase and ⁇ -amylase.
  • the amount of glucose was quantified with a glucose quantification kit (Wako Pure Chemical Industries), and the amylose concentration was obtained by multiplying the quantified value by the dilution factor. The results are shown in Table 4.
  • amylose-containing rayon fiber having an average molecular weight of 5.2 ⁇ 10 3 , elution of amylose was confirmed slightly. In contrast, 4.62 ⁇ 10 4 amylose-containing rayon fibers and 1.174 ⁇ 10 5 amylose-containing rayon fibers did not show any elution of amylose by washing.
  • Example 4 Production of amylose-containing rayon nonwoven fabric filter>
  • the amylose-containing rayon fiber (20% preparation) having an average molecular weight of 1.174 ⁇ 10 5 produced in Example 1-4 was processed into a nonwoven fabric having a thickness of about 3 mm by a needle punch method to obtain an amylose-containing rayon nonwoven fabric.
  • This nonwoven fabric was cut into a disk shape having a diameter of 7 cm to obtain an amylose-containing rayon nonwoven fabric filter (Example 4).
  • Examples 5-1 to 5-3 Increasing clathrate force by heat treatment of amylose-containing rayon fiber in alcohol-water mixed solution> Place 50 mg of the amylose-containing rayon fiber prepared in Example 1-4 and 3 mL of an aqueous solvent (50% by volume methanol aqueous solution, 50% by volume ethanol aqueous solution or 50% by volume 1-propanol aqueous solution) into a pressure-resistant glass test tube (10 mL) and seal tightly. And heated with a heat block at 130 ° C. for 30 minutes. The rayon fiber was taken out, suction filtered, heated in an oven at 50 ° C.
  • an aqueous solvent 50% by volume methanol aqueous solution, 50% by volume ethanol aqueous solution or 50% by volume 1-propanol aqueous solution
  • Example 6-1 to 6-3 Increasing clathrate force by spraying alcohol on amylose-containing rayon fiber, followed by heat treatment> About 1 mL of methanol, ethanol, or 1-propanol was sprayed onto 50 mg of the amylose-containing rayon fiber prepared in Example 1-4, sealed in a glass container, heated in an oven at 130 ° C. for 30 minutes, and then allowed to cool to room temperature. To cool. This was heated in an oven at 50 ° C. for 2 hours, dried, and then allowed to cool at room temperature, whereby an alcohol-treated amylose-containing rayon fiber (methanol spray: Example 6-1 and ethanol spray: Example 6). -2,1-propanol spraying: Example 6-3) was obtained. In the same manner as in Example 8 below, it is confirmed that the inclusion force of amylose-containing rayon fibers has been improved by this alcohol treatment.
  • Example 7 Increasing clathrate force due to alkali treatment of amylose-containing rayon fiber> 50 mg of the amylose-containing rayon fiber prepared in Example 1-4 was immersed in 3 mL of 1N NaOH aqueous solution at room temperature for 1 hour, taken out, and neutralized by adding 1N hydrochloric acid aqueous solution. This was taken out, washed with water, heated in an oven at 50 ° C. for 2 hours, dried, and then allowed to cool at room temperature to obtain an alkali-treated amylose-containing rayon fiber. In the same manner as in Example 8 below, it was confirmed that the inclusion force of the amylose-containing rayon fibers was improved by this alkali treatment.
  • Example 8 Evaluation of inclusion force of amylose-containing rayon fibers obtained in Examples 5-1 to 5-3> In evaluating the inclusion force, nonylphenol was used as a guest molecule.
  • each of the amylose-containing rayon fiber prepared in Example 1-4, the amylose-containing rayon fiber treated in Examples 5-1 to 5-3, or the control rayon fiber of Comparative Example 1-1 contains nonylphenol at a concentration of 100 ppm.
  • Each rayon fiber was impregnated with nonylphenol by immersing in 3 mL of 50% aqueous methanol solution at 25 ° C. for 15 hours.
  • the concentration of nonylphenol in the aqueous solution before and after soaking the rayon fiber was measured by liquid chromatography. From the difference in the amount of nonylphenol before and after the immersion, the adsorption rate of nonylphenol to the rayon fiber and the inclusion force of the rayon fiber were determined.
  • the conditions for liquid chromatography are as follows: TSKgel ODS-100Z (manufactured by TOSOH) was used as the column, UV detector SPD-6A (manufactured by Shimadzu Corporation) was used as the detector, and LC-6A (manufactured by Shimadzu Corporation) was used as the liquid feed pump.
  • the column was kept at 40 ° C., and 80% methanol was used as an eluent at a flow rate of 1.0 mL / min. The results are shown in Table 5.
  • the inclusion force (%) of the amylose-containing rayon fiber was calculated based on the above equation (3). That is, calculation was performed by subtracting the nonylphenol adsorption rate of the control rayon fiber from the nonylphenol adsorption rate of the amylose-containing rayon fiber.
  • Example 9 Evaluation of inclusion force of amylose-containing rayon fiber to nonylphenol>
  • Nonylphenol was used as an example of an environmental pollutant guest molecule.
  • Liquid chromatography conditions were as follows: TSKgel ODS-100Z (manufactured by TOSOH) was used as the column, UV detector SPD-6A (manufactured by Shimadzu Corporation) was used as the detector, and LC-6A (manufactured by Shimadzu Corporation) was used as the liquid feed pump.
  • the column was kept at 40 ° C., and 80% methanol was used as an eluent at a flow rate of 1.0 mL / min. The results are shown in Table 6.
  • amylose-containing rayon fiber can adsorb nonylphenol, and its adsorption amount is much higher than that of the control rayon fiber, which is about 4 times. From this result, it was found that the amylose-containing rayon fiber of Example 1-4 had an inclusion force of 16.0%.
  • Example 10 Examination of inclusion method of nonylphenol of amylose-containing rayon fiber> Place 50 mg of the amylose-containing rayon fiber prepared in Example 1-4 and 3 mL of 50% methanol aqueous solution containing nonylphenol at a concentration of 100 ppm into a pressure-resistant glass test tube (10 mL), and seal it with a heat block at 130 ° C. for 30 minutes. The mixture was allowed to cool to room temperature for 15 hours. The concentration of nonylphenol in this aqueous solution before and after soaking and heating the rayon fiber was measured by liquid chromatography. From the difference in the amount of nonylphenol before and after the immersion, the adsorption of nonylphenol to the rayon fiber was determined.
  • Liquid chromatography conditions were as follows: TSKgel ODS-100Z (manufactured by TOSOH) was used as the column, UV detector SPD-6A (manufactured by Shimadzu Corporation) was used as the detector, and LC-6A (manufactured by Shimadzu Corporation) was used as the liquid feed pump.
  • the column was kept at 40 ° C., and 80% methanol was used as an eluent at a flow rate of 1.0 mL / min. The results are shown in Table 7.
  • Example 11 Trial production of rayon fiber nonwoven fabric containing nonylphenol inclusion amylose>
  • Nonylphenol was used as an example of the guest molecule of the ultraviolet absorber.
  • the amylose-containing rayon nonwoven fabric having an average molecular weight of 1.174 ⁇ 10 5 produced in Example 4 was used.
  • the control rayon (without amylose) produced in Comparative Example 1-1 was processed into a nonwoven fabric having a thickness of about 3 mm by the needle punch method to obtain a control rayon nonwoven fabric without amylose.
  • These non-woven fabrics were cut into 1.5 cm square (weight 34 mg), and impregnated with nonylphenol by immersing in 5 mL of 50% aqueous methanol solution containing nonylphenol having a concentration of 100 ppm for 1 hour. Thereafter, the nonwoven fabric was taken out and suction filtered.
  • Example 11 a nonylphenol-encapsulated amylose-containing nonwoven fabric (Example 11) or a nonylphenol-treated control nonwoven fabric (Comparative Example 11-1) was obtained.
  • a nonwoven fabric similarly treated with an aqueous solution containing no nonylphenol was also prepared (amylose-containing rayon nonwoven fabric having an average molecular weight of 1.174 ⁇ 10 5 : Comparative Example 11-2; control rayon (without amylose): Comparative Example 11-3. ) was also produced.
  • Example 12 UV protection of nonylphenol inclusion amylose-containing rayon nonwoven fabric>
  • the rayon nonwoven fabric produced in Example 11 was tested for its ultraviolet protection effect by irradiating the rayon nonwoven fabric containing nonylphenol inclusion amylose with ultraviolet light and visible light of 200 nm to 450 nm and measuring the reflection spectrum.
  • the spectrum shown by the solid line in FIG. 1 is a spectrum of ultraviolet light and visible light absorbed by the nonylphenol-clad amylose-containing rayon nonwoven fabric.
  • the spectrum of the solid line was obtained by subtracting the absorption spectrum of the amylose-containing rayon nonwoven fabric treated with the aqueous solution containing no nonylphenol of Comparative Example 11-2 from the absorption spectrum of the nonylphenol-encapsulated amylose-containing nonwoven fabric prepared in Example 11.
  • the spectrum shown by the dotted line in FIG. 1 is a spectrum of ultraviolet light and visible light absorbed by a nonylphenol-treated control rayon nonwoven fabric.
  • the dotted line spectrum was obtained by subtracting the absorption spectrum of the control rayon nonwoven fabric treated with the aqueous solution containing no nonylphenol of Comparative Example 11-3 from the absorption spectrum of the nonwoven fabric of Comparative Example 11-1.
  • Example 11 As shown in FIG. 1, it was found that the control rayon nonwoven fabric treated with nonylphenol did not absorb ultraviolet light, while the nonylphenol-encapsulated amylose-containing rayon nonwoven fabric absorbed ultraviolet light at 280 nm. As a result, it was found that the nonylphenol-encapsulated amylose-containing rayon nonwoven fabric produced in Example 11 had an ultraviolet protection effect.
  • Example 13 Production of bactericide-containing amylose rayon fiber> Antibiotics are used as an example of the bactericide guest molecule.
  • amylose-containing rayon fiber (20% charged) having an average molecular weight of 1.174 ⁇ 10 5 produced in Example 1-4 or the control rayon fiber (containing no amylose) produced in Comparative Example 1-1 was added to the bactericide-containing solution.
  • the rayon fiber is impregnated with the disinfectant by dipping for a period of time. Thereafter, the rayon fiber is taken out and air-dried at room temperature overnight to obtain a fungicide-containing amylose rayon.
  • the results of the examples are compared with the control results to evaluate the inclusion force.
  • Example 14 Production of deodorant-containing amylose rayon fiber>
  • lauryl methacrylate is used as an example of the deodorant guest molecule.
  • the amylose-containing rayon fiber (20% preparation) having an average molecular weight of 1.174 ⁇ 10 5 produced in Example 1-4 or the control rayon fiber (containing no amylose) produced in Comparative Example 1-1 was added to the deodorant solution.
  • the rayon fiber is impregnated with the deodorant by dipping for a period of time. Thereafter, the rayon fiber is taken out and air-dried overnight at room temperature to obtain a deodorant-containing amylose rayon.
  • the results of the examples are compared with the control results to evaluate the inclusion force.
  • Example 15 Deodorizing function of amylose rayon fiber>
  • the amylose rayon nonwoven fabric filter produced in Example 4 or the control rayon nonwoven fabric filter (without amylose) produced in Example 10 is placed in a closed container containing malodorous substances (nonenal, butyric acid, valeric acid, isovaleric acid). Leave for 2 and 24 hours. Thereafter, the amount of malodorous substances contained in the air in the container before and after inserting the nonwoven fabric filter is measured by gas chromatography and compared.
  • malodorous substances nonenal, butyric acid, valeric acid, isovaleric acid
  • Example 16 Production of insecticide-containing amylose rayon fiber> Pyrethroid is used as an example of a guest molecule of an insect repellent.
  • amylose-containing rayon (20% preparation) fiber having an average molecular weight of 1.174 ⁇ 10 5 produced in Example 1-4 or the control rayon (containing no amylose) produced in Comparative Example 1-1 was added to the insecticide-containing solution for 1 hour.
  • the insect repellent is impregnated by dipping. Thereafter, the rayon fiber is taken out and air-dried overnight at room temperature to obtain an insecticide-containing amylose rayon.
  • the results of the examples are compared with the control results to evaluate the inclusion force.
  • Example 17 Concentration, recovery, removal, and purification of chemical substances using amylose rayon fiber>
  • the amylose rayon produced in Example 1-4 or the rayon produced in Comparative Example 1-1 (control) is placed in a bath containing nonylphenol and left overnight. Thereafter, the rayon is taken out, washed with water, and eluted with a small amount of methanol to concentrate and recover the target chemical substance.
  • Example 18 Stabilization of pigment contained in amylose rayon fiber>
  • a dye is used as an example of a substance (guest molecule) intended to be stabilized.
  • amylose-containing rayon (20% charged) fiber having an average molecular weight of 1.174 ⁇ 10 5 produced in Example 1-4 or the control rayon (without amylose) produced in Comparative Example 1-1 was immersed in the guest substance solution for 1 hour. By so doing, the pigment is impregnated. Thereafter, the rayon fiber is taken out and air-dried overnight at room temperature to obtain a guest substance-containing amylose rayon.
  • the thus obtained guest substance-containing amylose rayon is irradiated with ultraviolet rays for 6 hours, and thereafter, how much guest substance remains is examined.
  • the same amount of ultraviolet light is also applied to the guest material which is not included.
  • the stabilization of the guest material is evaluated by comparing the remaining amount of the guest material in comparison with the examples.
  • Example 2 Synthesis of amylose> To a reaction solution (1 liter) containing 20 mM phosphate buffer (pH 7.0), 20 g / L sucrose, and a maltooligosaccharide mixture (245 mg / liter), Example 2-1A in WO 2004/113525 pamphlet Potato tuber-derived thermostable glucan phosphorylase (having the amino acid sequence of SEQ ID NO: 34 of WO 2004/113525 pamphlet; 1 unit / ml) prepared and purified according to the method described in JP 2005 / Thermostable Streptococcus mutans-derived sucrose phosphorylase (having the amino acid sequence of SEQ ID NO: 22 of WO 2005/24008 pamphlet) prepared according to the method described in Example 2A of No.
  • Potato tuber-derived thermostable glucan phosphorylase having the amino acid sequence of SEQ ID NO: 34 of WO 2004/113525 pamphlet; 1 unit / ml
  • Examples 19-1 and 19-2 Production of amylose-containing rayon fibers having an average molecular weight of 3.00 ⁇ 10 4 > Viscose was prepared from raw pulp (LDPT: Nippon Paper Chemicals) according to a conventional method. This viscose had a cellulose content of 9% by weight, an alkali content of 5% by weight and a falling ball viscosity of 60 seconds.
  • LDPT Nippon Paper Chemicals
  • An enzyme-synthesized amylose with an average molecular weight of 3.00 ⁇ 10 4 (not including a branched structure) synthesized in Synthesis Example 2 was dissolved in a 5 wt% NaOH aqueous solution to prepare an alkaline aqueous solution of amylose.
  • This aqueous alkaline solution and viscose were mixed according to a conventional method and then spun to obtain an amylose-containing rayon fiber.
  • the amount ratio (weight ratio) of amylose and cellulose was changed as shown in Table 9 below.
  • the amylose content in the amylose-containing rayon fiber was quantified by the following method. After dissolving 20 mg of amylose-containing rayon fibers in a copper ammonia solution, only cellulose was reprecipitated by diluting with an acetic acid solution simultaneously with neutralization (total 2 mL). The mixture was centrifuged at 13,200 ⁇ g for 10 minutes, and the amount of amylose in the supernatant was quantified by the phenol sulfate method. The results are shown in Table 9.
  • amylose having an average molecular weight of 3.00 ⁇ 10 4 or more can be contained in the rayon.
  • Example 20 Inclusion of nonylphenol with amylose-containing rayon fibers produced in Examples 19-1 and 19-2> The inclusion force of rayon fibers containing amylose with an average molecular weight of 3.00 ⁇ 10 4 produced in Examples 19-1 and 19-2 was examined using nonylphenol as a guest substance. As a control, the inclusion force of the rayon fiber produced in Comparative Example 1-1 was also measured. The nonylphenol clathrate operation method and the clathrate force evaluation method were the same as in Example 2. The results are shown in Table 10.
  • amylose-containing rayon fibers having an average molecular weight of 3.00 ⁇ 10 4 in Examples 19-1 and 19-2 also had an inclusion force.
  • the inclusion force was lower than the results of Examples 1-1 to 1-4 in Table 3. It was confirmed that the molecular weight of amylose affects the inclusion force, and that the inclusion force increases as the molecular weight increases.
  • Example 15 the deodorization test was performed in the state of the nonwoven fabric, but in the following Examples 21 and 24, the deodorization test was performed in the form of cotton, and in Example 23, the condition of the fabric was performed.
  • Example 21 Evaluation of deodorizing ability of amylose-containing rayon fiber> The deodorizing ability of the amylose-containing rayon fiber of Example 1-4 and the control rayon ray of Comparative Example 1-1 was measured using pelargonic acid and nonenal as guest substances. These rayon fibers were used in the cotton state. Pelargonic acid and nonenal are typical malodorous substances. Pelargonic acid is a substance with an unpleasant odor such as a rotting odor and is used in the production of plasticizers, lacquers, adhesives, alkyd resins and softeners. Furthermore, pelargonic acid is known as a causative substance of malodors emitted by men in their 30s. Nonenal is known as a causative substance of aging odor, which is a body odor peculiar to middle-aged and elderly people.
  • Gas chromatography conditions are as follows: DB-WAX (J & W) was used as the column, and mass spectrometer GC-MS5050A (Shimadzu Corporation) was used as the measuring instrument. The column was kept at 200 ° C. and helium was used as the carrier gas.
  • the evaluation of the deodorizing power was calculated by the deodorizing rate of pelargonic acid and nonenal to rayon obtained by the following formula.
  • the deodorization rate with respect to pelargonic acid of the amylose-containing rayon fiber of Example 1-4 was 66.5%, and it was found that the amylose-containing rayon fiber had a very excellent deodorizing power with respect to pelargonic acid.
  • the deodorization rate of the amylose-containing rayon fiber of Example 1-4 with respect to nonenal was 41.2%, and it was found that the amylose-containing rayon fiber had an excellent deodorizing power with respect to nonenal.
  • Example 22 Production of amylose-containing rayon dough> A 60% blended yarn was produced by blending 30% by weight of the amylose-containing rayon fibers of Examples 1-1 and 1-2 and 70% by weight of the rayon fiber of Comparative Example 1-1. Using this, a tubular knitted fabric was produced (amylose-containing rayon fabric of Example 22). For comparison, a tubular knitted fabric (Comparative Example 22) was produced in the same manner except that no amylose-containing rayon fiber was blended.
  • Example 23 Evaluation of deodorizing ability of amylose-containing rayon dough> The deodorizing power of the amylose-containing rayon fabric prepared in Example 22 and the control rayon fabric was measured using pelargonic acid and nonenal as guest substances.
  • Gas chromatography conditions are as follows: DB-WAX (J & W) was used as a column, and mass spectrometer GC-MS5050A (manufactured by Shimadzu Corporation) was used as a measuring instrument. The column was kept at 200 ° C. and helium was used as the carrier gas.
  • deodorizing power was calculated by the deodorizing rate of pelargonic acid and nonenal to the dough obtained by the following formula.
  • the deodorization rates with respect to pelargonic acid of the amylose-containing rayon doughs of Examples 22-1 and 22-2 are 83.2% and 92.1%, respectively, which are higher than the control rayon dough (Comparative Example 22). It was found to have deodorant power. This deodorizing power increased with increasing amylose content.
  • the deodorization rates of the amylose-containing rayon doughs of Examples 22-1 and 22-2 with respect to Nonenal were 73.0% and 76.1%, respectively, which was higher than that of the control rayon dough (Comparative Example 22). It was found to have odor power. This deodorizing power increased with increasing amylose content.
  • Example 24 Inclusion of aroma component menthol with amylose-containing rayon fiber> The inclusion force of the amylose-containing rayon fibers prepared in Example 1-2, Example 1-4, Example 19-1, and Example 19-2 and the control rayon fiber prepared in Comparative Example 1-1 was used as a guest substance. Evaluation was performed using menthol. These rayon fibers were used in the cotton state
  • Gas chromatography conditions are as follows: GC-2014 (manufactured by Shimadzu Corporation) for the gas chromatograph device, ULBONHR-Thermon-600T (0.25 mm ⁇ ⁇ 25 m, manufactured by Shinwa Kako) for the column, helium gas for the carrier gas, and hydrogen ionization detector for the detector (Shimadzu Corporation) Made).
  • the vaporization chamber temperature was 280 ° C.
  • the column temperature was 150 ° C.
  • the detector temperature was 250 ° C.
  • the carrier gas pressure was kept at 150 kPa.
  • Table 15 The results are shown in Table 15.
  • amylose-containing rayon fibers prepared in Examples 19-1, 19-2, 1-2, and 1-4 with respect to menthol were 5.0%, 8.0%, 5.5%, and 4.%, respectively.
  • the content was 2%, 4 to 8 times higher than that of the control rayon fiber (Comparative Example 1-1).
  • amylose-containing rayon fibers can include menthol.
  • Example 25 Preparation of thermal bond nonwoven fabric of amylose-containing rayon fiber> 40% by weight of the amylose-containing rayon fiber having an average molecular weight of 1.174 ⁇ 10 5 prepared in Example 1-4 and 60% by weight of polypropylene / polyethylene core-sheath fiber (ES fiber manufactured by Chisso) were opened by air flow, After mixing and producing a web with a card machine, a thermal bond nonwoven fabric (about 20 g / m 2 ) (Example 25) was produced by heating with a heat roll. For comparison, a thermal bond nonwoven fabric (about 20 g / m 2 ) of polypropylene / polyethylene core-sheath fiber not containing amylose-containing rayon fiber (Comparative Example 25) was produced.
  • Example 26 Inclusion of aroma component menthol to the thermal bond nonwoven fabric produced in Example 25> 6.5 mL of a 2% menthol methanol solution was added to 1.3 g of each of the thermal bond nonwoven fabric containing 40% amylose-containing rayon fiber prepared in Example 25 and the control thermal bond nonwoven fabric prepared in Comparative Example 25, and the oven was heated at 100 ° C. Dry in to evaporate the solvent and excess menthol. After 15 hours, a thermal bond nonwoven fabric containing 40% amylose-containing rayon fibers encased in menthol and a control thermal bond nonwoven fabric were obtained.
  • thermo bond nonwoven fabric (Comparative Example 25) could not hold menthol at all, whereas the thermal bond nonwoven fabric of Example 25 containing 40% amylose-containing rayon fiber could contain 2.5% menthol. there were. Thus, it turned out that the thermal bond nonwoven fabric containing an amylose containing rayon fiber can include menthol.
  • Example 27 Menthol retention stability of thermal bond nonwoven fabric containing 40% menthol-containing amylose-containing rayon fiber prepared in Example 26>
  • the menthol clathrate amylose-containing rayon fiber 40% blended thermal bond nonwoven fabric produced in Example 26 can stably hold menthol at a temperature of 25 ° C. to 100 ° C. under conditions of a humidity of 30% or less. I understood.
  • Example 28 Menthol sustained release property of thermal bond nonwoven fabric containing 40% menthol-containing amylose-containing rayon fiber prepared in Example 26> The sustained release property of the menthol clathrate amylose-containing rayon fiber 40% blended thermal bond nonwoven fabric prepared in Example 26 under humidified conditions was examined.
  • a menthol clathrated amylose-containing rayon-containing nonwoven fabric was spread in a thermo-hygrostat and allowed to stand, and the change over time in the amount of menthol in the nonwoven fabric was examined. Temperature and humidity were set to 50% at 25 ° C, 80% at 25 ° C or 80% at 37 ° C.
  • Example 26 The results are shown in FIG. As shown in FIG. 3, the menthol clathrate amylose-containing rayon fiber 40% blended thermal bond nonwoven fabric produced in Example 26 did not release menthol even after 5 hours in an environment of temperature 25 ° C. and humidity 50%. However, when the humidity was increased to 80%, menthol was gradually released over time. When the temperature was raised to 37 ° C. with the humidity kept at 80%, the release rate of menthol increased, and about 35% of the included menthol was released after 5 hours.
  • the menthol a guest substance encapsulated in an amylose-containing rayon-blended thermal bond nonwoven fabric, exhibits sustained release properties that are gradually released by changing the humidity conditions.
  • Example 29 Inclusion of aromatic component linalool with amylose-containing rayon fiber> The inclusion force of the amylose-containing rayon fiber produced in Example 1-4 and the control rayon fiber produced in Comparative Example 1-1 was evaluated using linalool as a guest substance. These rayon fibers were used in the cotton state.
  • amylose-containing rayon fibers can include linalool.
  • Example 30 Inclusion of aromatic component Menton by amylose-containing rayon fiber> The inclusion force of the amylose-containing rayon fiber produced in Example 1-2 and the control rayon fiber produced in Comparative Example 1-1 was evaluated using a ketone-based fragrance menton as a guest substance. These rayon fibers were used in the cotton state.
  • amylose-containing rayon fibers can include menthone.
  • Example 31 Inclusion of aroma component citronellal with amylose-containing rayon fiber> The inclusion force of the amylose-containing rayon fiber produced in Example 1-2 and the control rayon fiber produced in Comparative Example 1-1 was evaluated using an aldehyde-based fragrance citronellal as a guest substance. These rayon fibers were used in the cotton state.
  • amylose-containing rayon fibers can include citronellal.
  • Example 32 Inclusion of aroma component nonanal with amylose-containing rayon fiber> The inclusion force of the amylose-containing rayon fiber produced in Example 1-2 and the control rayon fiber produced in Comparative Example 1-1 was evaluated using aldehyde perfume nonanal as a guest substance. These rayon fibers were used in the cotton state.
  • Example 1-2 To 100 mg of the amylose-containing rayon fiber produced in Example 1-2 and the control rayon fiber produced in Comparative Example 1-1, 800 ⁇ L each of a 2% nonanal methanol solution was added and dried in an oven at 100 ° C. And excess nonanal was volatilized. After 14 hours, it was removed from the oven, and amylose-containing rayon and control rayon fibers enclosing nonanal were obtained.
  • amylose-containing rayon fibers can include nonanal.
  • Example 33 Inclusion of aromatic component geraniol with amylose-containing rayon fiber> The inclusion force of the amylose-containing rayon fiber produced in Example 1-2 and the control rayon fiber produced in Comparative Example 1-1 was evaluated using an alcohol-based fragrance geraniol as a guest substance. These rayon fibers were used in the cotton state.
  • amylose-containing rayon fibers can include geraniol.
  • Example 34 Inclusion of aromatic component citronellol with amylose-containing rayon fiber> The inclusion force of the amylose-containing rayon fiber produced in Example 1-2 and the control rayon fiber produced in Comparative Example 1-1 was evaluated using an alcohol-based fragrance citronellol as a guest substance. These rayon fibers were used in the cotton state.
  • amylose-containing rayon fibers can include citronellol.
  • Example 35 Inclusion of aromatic component linalyl acetate with amylose-containing rayon fiber> The inclusion force of the amylose-containing rayon fiber produced in Example 1-2 and the control rayon fiber produced in Comparative Example 1-1 was evaluated using the ester-based fragrance linalyl acetate as a guest substance. These rayon fibers were used in the cotton state.
  • amylose-containing rayon fibers can include linalyl acetate.
  • Example 36 Sustained release of menthol from amylose-containing rayon fiber clathrated with menthol> The influence of the degree of polymerization of amylose on the sustained release of menthol from amylose-containing rayon encapsulated with menthol was examined.
  • Example 19-2 To each 100 mg of the amylose-containing rayon fibers prepared in Example 1-2, Example 1-4, and Example 19-2, 800 ⁇ L of a 2% menthol methanol solution was added and dried in an oven at 100 ° C. And excess menthol was volatilized. After 15 hours, it was taken out from the oven, and amylose-containing rayon fibers enclosing menthol were obtained.
  • menthol clathrate amylose-containing rayon fibers were examined for sustained release under humidified conditions.
  • the menthol clathrate amylose-containing rayon fiber was spread in a thermo-hygrostat and allowed to stand, and after 4 hours, the amount of menthol in the fiber was examined. Temperature and humidity were set to 50% at 37 ° C or 80% at 37 ° C.
  • the extraction method and analysis method of menthol were the same as in Example 24. The results are shown in Table 24.
  • the menthol clathrate amylose-containing rayon fiber released only 0 to 0.11 mg of menthol even after 4 hours in an environment of a temperature of 37 ° C. and a humidity of 50%, but the humidity was 80%. To 1.2 to 1.6 mg of menthol was released. There was no particular relationship with the degree of amylose polymerization regarding the amount of menthol released. As described above, it was found that the menthol of the guest substance included in the amylose-containing rayon fiber was gradually released by increasing the humidity within the tested range regardless of the polymerization degree of the contained amylose.
  • Example 37 Slow release of fragrance component from amylose-containing rayon fiber including fragrance component> Example 29 (linalool), Example 30 (menton), Example 31 (citronellal), Example 32 (nonanal), Example 33 (geraniol), Example 34 (citronellol) and Example 35 (linalyl acetate)
  • Example 29 (linalool), Example 30 (menton), Example 31 (citronellal), Example 32 (nonanal), Example 33 (geraniol), Example 34 (citronellol) and Example 35 (linalyl acetate)
  • Example 36 there was almost no difference in sustained release depending on the molecular weight of amylose in the range of average molecular weight of 3.00 ⁇ 10 4 to 1.174 ⁇ 10 5 .
  • the sustained release property was examined by using amylose-containing rayon fiber as a representative.
  • Each aromatic component inclusion amylose-containing rayon fiber was spread in a thermo-hygrostat and allowed to stand, and after 4 hours, the amount of each aromatic component in each fiber was examined. Temperature and humidity were set to 50% at 37 ° C or 80% at 37 ° C.
  • Example 29 Lialool
  • Example 30 Methyl
  • Example 31 Citronellal
  • Example 32 Nonanar
  • Example 33 Garaniol
  • Example 34 Same as (citronellol) and Example 35 (linalyl acetate).
  • the release rate (%) of each fragrance component was determined by the following formula. The results are shown in Table 25.
  • Example 29 (linalool), Example 30 (menton), Example 31 (citronellal), Example 32 (nonanal), Example 33 (geraniol), Example 34 (citronellol) and practice.
  • Each aroma component-containing amylose-containing rayon fiber produced in Example 35 did not release each aroma component even after 4 hours in an environment of a temperature of 37 ° C. and a humidity of 50%. Increasing the humidity to 80% released 19.0-37.9% of the fragrance component.
  • the amount of menthol included in the amylose-containing rayon fiber was compared with the amount included in the amylose powder.
  • amylose-containing rayon fibers produced in Example 1-2, Example 1-4, and Example 19-2, the control rayon fiber produced in Comparative Example 1-1, and the average molecular weight of 4.62 synthesized in Synthesis Example 1 800 ⁇ L of a 2% menthol methanol solution was added to 100 mg each of ⁇ 10 4 or 1.174 ⁇ 10 5 enzyme-synthesized amylose and enzyme-synthesized amylose with an average molecular weight of 3.00 ⁇ 10 4 synthesized in Synthesis Example 2, and 100 ° C. And dried in an oven to volatilize the solvent and excess menthol.
  • the amount obtained by subtracting the menthol content of the control fiber from the actual menthol content of the amylose-containing rayon fiber indicates the menthol content by amylose contained in the rayon fiber. If there is no change in the inclusion ability of amylose even if amylose is contained in rayon fiber (that is, if there is no synergistic effect between amylose and rayon fiber), the menthol content per gram of amylose will be Should be the same as menthol content. However, as shown in Table 26, when the menthol content per weight of amylose is compared, the menthol content is significantly increased when amylose is contained in the rayon fiber.
  • the inclusion amount of menthol per weight of amylose was about 620 mg of enzyme-synthesized amylose having an average molecular weight of 4.62 ⁇ 10 4 , 1.174 ⁇ 10 5 , and 3.00 ⁇ 10 4. 15 times, about 7.4 times, and about 31 times, it can be seen that by adding the enzyme-synthesized amylose to the rayon fiber, it is remarkably increased. Therefore, it was found that inclusion of amylose in rayon fibers improved the amylose inclusion ability, and the effect was synergistic.
  • Example 39 Comparison of inclusion ability of aromatic component between amylose-containing rayon fiber and amylose powder> The amount of menthol included in the amylose-containing rayon fiber was compared with the amount included in the amylose powder. As confirmed in Example 38, in the range of average molecular weight of 3.00 ⁇ 10 4 to 1.174 ⁇ 10 5 , any molecular weight of amylose was included in rayon, so that the inclusion amount per weight of amylose. Therefore, the amylose-containing rayon fiber of Example 1-2 and the enzyme-synthesized amylose powder of Sample 2 having an average molecular weight of 4.62 ⁇ 10 4 were examined here. That is, in any sample, the average molecular weight of amylose was 4.62 ⁇ 10 4 .
  • Table 1-2 shows 2% of 100 mg each of the enzyme-synthesized amylose synthesized in Example 1-2 and Synthesis Example 1 (sample 2) having an average molecular weight of 4.62 ⁇ 10 4 and the control rayon fiber prepared in Comparative Example 1-1. Then, 800 ⁇ L of a methanol solution containing each fragrance component shown in (1) was added and dried in an oven at 50 ° C. (linalyl acetate) or 100 ° C. (other than linalyl acetate) to volatilize the solvent and excess fragrance components. After 15 hours, the amylose-containing rayon fiber, control rayon fiber, and enzyme-synthesized amylose powder were obtained. The aroma component content of each rayon fiber was examined.
  • Example 29 Lialool
  • Example 30 Methyl
  • Example 31 Citronellal
  • Example 32 Nonanar
  • Example 33 Garaniol
  • Example 34 Same as (citronellol) and Example 35 (linalyl acetate).
  • Table 27 The results are shown in Table 27.
  • the amount obtained by subtracting the fragrance component content of the control fiber from the actual fragrance component content of the amylose-containing rayon fiber indicates the fragrance component content of amylose contained in the rayon fiber. If there is no change in the inclusion ability of amylose even if amylose is contained in the rayon fiber (that is, if there is no synergistic effect between amylose and rayon fiber), the fragrance component content per gram of amylose is amylose alone. Should be the same as the aroma content. However, as shown in Table 27, when comparing the fragrance component content per weight of amylose when the same fragrance component is included, the fragrance component content is greater when amylose is contained in the rayon fiber. It has increased remarkably.
  • the inclusion amount of each fragrance component per amylose weight is about 5.1 times (geraniol) to about 15.9 times (nonanal) per amylose weight by inclusion in rayon fiber. It can be seen that the number increases significantly. Therefore, it was found that inclusion of amylose in rayon fiber improved the inclusion ability of amylose and the effect was synergistic.
  • This rayon fiber holds amylose stably, and does not elute amylose even in operations such as washing, and can withstand repeated use. Further, the present rayon fiber is contained in a state in which amylose can exert an inclusion function, and an additional function can be imparted to the fiber by adding various guest substances.

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Abstract

L'invention porte sur un procédé pour la production de fibres de rayonne contenant de l'amylose, qui comprend une étape consistant à mélanger une solution aqueuse alcaline d'un amylose avec de la viscose pour préparer une solution mélangée et une étape consistant à filer la solution mélangée pour produire les fibres de rayonne contenant de l'amylose, l'amylose étant un amylose synthétisé par voie enzymatique ayant une masse moléculaire moyenne de 3 × 104 à 2 × 105 inclus. Par exemple, on peut produire des fibres de rayonne contenant de l'amylose aptes à incorporer une substance invitée, l'amylose dans les fibres de rayonne ne pouvant pas être sensiblement élué par lavage, étant dispersé dans les fibres de rayonne, étant un amylose synthétisé par voie enzymatique ayant une masse moléculaire moyenne en poids de 3 × 104 à 2 × 105 inclus et ne comprenant aucune substance invitée.
PCT/JP2010/004067 2009-06-18 2010-06-17 Fibres contenant de l'amylose, leur procédé de production et leur utilisation Ceased WO2010146873A1 (fr)

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