WO2013039070A1 - 親水性化セルロース繊維の製造方法 - Google Patents
親水性化セルロース繊維の製造方法 Download PDFInfo
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- WO2013039070A1 WO2013039070A1 PCT/JP2012/073217 JP2012073217W WO2013039070A1 WO 2013039070 A1 WO2013039070 A1 WO 2013039070A1 JP 2012073217 W JP2012073217 W JP 2012073217W WO 2013039070 A1 WO2013039070 A1 WO 2013039070A1
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- WIPO (PCT)
- Prior art keywords
- cellulose fiber
- reaction solution
- producing
- hydrophilic
- oxidized
- Prior art date
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- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 217
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 54
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- 238000000034 method Methods 0.000 claims abstract description 73
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- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 25
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 101
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- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical group CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 claims description 6
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- 238000000402 conductometric titration Methods 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HFCSXCKLARAMIQ-UHFFFAOYSA-L disodium;sulfate;hydrate Chemical compound O.[Na+].[Na+].[O-]S([O-])(=O)=O HFCSXCKLARAMIQ-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- PGBHMTALBVVCIT-VCIWKGPPSA-N framycetin Chemical compound N[C@@H]1[C@@H](O)[C@H](O)[C@H](CN)O[C@@H]1O[C@H]1[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](N)C[C@@H](N)[C@@H]2O)O[C@@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CN)O2)N)O[C@@H]1CO PGBHMTALBVVCIT-VCIWKGPPSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- AAUNBWYUJICUKP-UHFFFAOYSA-N hypoiodite Chemical compound I[O-] AAUNBWYUJICUKP-UHFFFAOYSA-N 0.000 description 1
- GEOVEUCEIQCBKH-UHFFFAOYSA-N hypoiodous acid Chemical compound IO GEOVEUCEIQCBKH-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 description 1
- KAGBQTDQNWOCND-UHFFFAOYSA-M lithium;chlorite Chemical compound [Li+].[O-]Cl=O KAGBQTDQNWOCND-UHFFFAOYSA-M 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- NWAPVVCSZCCZCU-UHFFFAOYSA-L magnesium;dichlorite Chemical compound [Mg+2].[O-]Cl=O.[O-]Cl=O NWAPVVCSZCCZCU-UHFFFAOYSA-L 0.000 description 1
- YZQBYALVHAANGI-UHFFFAOYSA-N magnesium;dihypochlorite Chemical compound [Mg+2].Cl[O-].Cl[O-] YZQBYALVHAANGI-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BSGGVIDZMMSWKM-UHFFFAOYSA-L strontium dichlorite Chemical compound [Sr+2].[O-]Cl=O.[O-]Cl=O BSGGVIDZMMSWKM-UHFFFAOYSA-L 0.000 description 1
- DFKCZMNZBDPBGG-UHFFFAOYSA-N strontium dihypochlorite Chemical compound [Sr++].[O-]Cl.[O-]Cl DFKCZMNZBDPBGG-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
Images
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/28—Polysaccharides or their derivatives
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/44—Medicaments
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
- C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/01—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/30—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with oxides of halogens, oxyacids of halogens or their salts, e.g. with perchlorates
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/34—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxygen, ozone or ozonides
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/54—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur dioxide; with sulfurous acid or its salts
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
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- D06M13/388—Amine oxides
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/04—Materials for stopping bleeding
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Definitions
- the present invention relates to a method for producing a hydrophilic cellulose fiber, and more particularly to a method for producing a hydrophilic cellulose fiber by oxidizing a part of the hydroxyl group of the cellulose fiber to a carboxyl group.
- cotton apparel products such as underwear (cellulose fiber products) have been required to have high moisture absorption and moisture release.
- Examples of a method for obtaining a cotton apparel product (cellulose fiber product) having such a high hygroscopic property and a moisture releasing property include a method of hydrophilizing cellulose fiber as a raw material.
- Various methods for hydrophilizing cellulose fibers are known. A typical example is a method of oxidizing a hydroxyl group of cellulose to a carboxyl group.
- a reaction comprising an N-oxyl compound such as 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and a halogen-based oxidizing agent is used.
- N-oxyl compound such as 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)
- TEMPO 2,2,6,6-tetramethylpiperidine-N-oxyl
- Item 4. Item 2. The method for producing a hydrophilic cellulose fiber according to Item 1, wherein the step (1b) is performed twice or more.
- Item 5. Item 3. The method for producing a hydrophilic cellulose fiber according to Item 1 or 2, wherein the oxidizing agent used in the step (1a) and / or the step (1b) is a halogen acid oxidizing agent.
- Item 7. (2) The hydrophilized cellulose fiber according to any one of Items 1 to 4, further comprising a step of oxidizing the oxidized cellulose fiber obtained in steps (1a) and (1b) in a reaction solution containing an oxidizing agent. Manufacturing method.
- Item 9. Item 7.
- Item 10. (3) The method for producing a hydrophilic cellulose fiber according to any one of Items 5 to 7, further comprising a step of dehalogenating the oxidized cellulose fiber obtained in the step (2) with a dehalogenating agent.
- Item 11. (4a) The method for producing a hydrophilic cellulose fiber according to any one of Items 5 to 7, further comprising a reduction treatment step of reducing the oxidized cellulose fiber obtained in the step (2) in a reaction solution containing a reducing agent. .
- the reducing agent is any one of Items 9 to 12, wherein the reducing agent is at least one selected from the group consisting of thiourea, hydrosulfite, sodium hydrogen sulfite, sodium borohydride, sodium cyanoborohydride, and lithium borohydride.
- an initial oxidation treatment of cellulose fibers is performed by reusing the reaction solution used in the oxidation step with an N-oxyl compound and an oxidizing agent in the presence of sodium sulfate. More cellulose groups can be substituted with cellulose fibers than the introduction of carboxyl groups by the method, and the reaction efficiency of the carboxyl groups can be improved.
- the reaction solution used in the oxidation step it is possible to reuse the reaction solution without discarding the N-oxyl compound used as a catalyst and sodium sulfate used as a co-catalyst. It is also useful from an economic point of view.
- it is a graph which shows an example of the relationship between the content rate of sodium sulfate, and the introduction amount of the COOH group to a cellulose fiber.
- 2 is a micrograph of a fiber cross section of a sample obtained in Example 1.
- FIG. 2 is a photograph showing the Pb distribution of the fiber cross section of the sample obtained in Example 1.
- FIG. 2 is a photomicrograph of a fiber cross section of a sample obtained in Comparative Example 1.
- 6 is a photograph showing a Pb distribution of a fiber cross section of a sample obtained in Comparative Example 1.
- the raw material cellulose fiber used in the method for producing a hydrophilic cellulose fiber of the present invention may be a natural cellulose fiber such as a plant, animal, or bacteria-producing gel, or a regenerated cellulose fiber.
- natural cellulose fibers such as cotton, hemp, pulp, and bacterial cellulose, and regenerated cellulose fibers such as rayon and cupra can be used.
- the rayon include viscose rayon, copper ammonia rayon, and polynosic rayon.
- the form of the raw material cellulose fiber is not limited to a fabric such as a woven or knitted fabric or a non-woven fabric, but may be a filamentous material such as a filament, staple or string.
- the structural structure of the fiber may be a blended fiber, a blended fiber, a blended fabric, a woven fabric, or a knitted fabric.
- the raw material cellulose fiber is preferably washed and scoured in advance from the viewpoint that the cellulose fiber can be sufficiently rendered hydrophilic in the subsequent steps and the bleaching effect can be sufficiently exhibited.
- “scouring” refers to a process of removing impurities contained in natural fibers, oil added at the spinning and knitting stage, machine oil adhering to the work process, iron rust, and the like.
- an oxidant such as a halogen-based oxidant is consumed in the oxidation treatment step with the N-oxyl compound and the oxidant, whereby a salt is generated as a by-product.
- the salt inhibits the reaction of the cocatalyst included in the oxidation step, it is known that the reaction efficiency decreases when the reaction solution used in the oxidation step is reused.
- the reaction solution can be reused by oxidation treatment.
- Sodium sulfate used in step (1a) may be an anhydride or a hydrate.
- Examples of sodium sulfate hydrate include sodium sulfate decahydrate (bow glass).
- the content of sodium sulfate in the step (1a) is preferably about 0.1 to 200 g / L, more preferably about 0.33 to 100 g / L in the reaction solution, and about 3.3 to 33.3 g / L. More preferred is about 4.5 to 10 g / L.
- the effect that the efficient TEMPO oxidation reaction which suppressed the polymerization degree fall of the cellulose fiber advances is acquired by setting the content rate of sodium sulfate to about 200 g / L or less.
- An example of the relationship between the content ratio of sodium sulfate and the amount of COOH group introduced into the cellulose fiber is shown in FIG.
- the content ratio of sodium sulfate in the reaction solution is preferably about 0.1 to 600% owf, more preferably about 1 to 300% owf, and still more preferably about 10 to 100% owf.
- the content ratio of sodium sulfate is preferably about 0.1% owf or more, the amount of COOH groups introduced to the cellulose fiber is likely to increase, and the resulting softness of the oxidized cellulose fiber becomes soft. It is done.
- the content ratio of sodium sulfate to about 600% owf or less, it is possible to suppress a decrease in the degree of polymerization of cellulose fibers, and an effect that an efficient TEMPO oxidation reaction proceeds can be obtained.
- the unit “% owf” represents weight% with respect to the fiber weight, and has the same meaning hereinafter.
- the N-oxyl compound contained in the reaction solution is used as a catalyst when oxidizing cellulose fibers.
- Specific examples of the N-oxyl compound include those represented by the general formula (I): (In the formula (I), R 1 to R 4 are the same or different and each represents a lower alkyl group having about 1 to 4 carbon atoms; R 5 and R 6 are the same or different and each represents a hydrogen atom; an acetylamino group; Carboxyl group; phosphonooxy group; amino group; 2-halogenated acetylamino group substituted by halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom); hydroxy group; about 1 to 4 carbon atoms An adamantane group, and R 5 and R 6 may be bonded to each other by an oxygen atom to form an oxo group), and formula (II): (In formula (II), R 7 and R 8 are the same or different and each represents a hydrogen atom
- N-oxyl compounds include 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), TEMPO derivatives having various functional groups at the 4-position carbon of TEMPO, 2-azaadamantane- N-oxyl and the like can be mentioned.
- TEMPO derivative include 4-acetamido TEMPO, 4-carboxy TEMPO, 4-phosphonooxy TEMPO, 4-amino-TEMPO, 4- (2-bromoacetamido) -TEMPO, 4-hydroxy TEMPO, 4-oxy TEMPO, 4-methoxy TEMPO, etc. are mentioned.
- TEMPO, 4-methoxy TEMPO and 4-acetamido TEMPO are preferable because of a high reaction rate for oxidizing the carbon at the 6-position of the glucose unit of the cellulose fiber.
- a catalytic amount is sufficient for the content of the N-oxyl compound, and specifically, it is preferably about 0.01 to 3 g / L in the reaction solution. Further, the content of the N-oxyl compound is more preferably about 0.1 to 2 g / L because it does not greatly affect the degree of hydrophilic treatment and the quality of the obtained cellulose fiber. Further, the content ratio of the N-oxyl compound in the reaction solution is preferably about 0.03 to 9.0% owf, more preferably about 0.75 to 6.0% owf.
- a halogen acid-based oxidizing agent is preferable, and hypohalous acid, halogenated isocyanuric acid or a salt thereof is more preferable.
- the halogen in the hypohalous acid include chlorine, bromine, and iodine.
- Specific examples of the hypohalous acid include hypochlorous acid, hypobromous acid, and hypoiodous acid.
- the metal salt forming the hypohalite include alkali metal salts such as lithium, potassium and sodium; alkaline earth metal salts such as calcium, magnesium and strontium.
- the salt of ammonium and hypohalous acid is also mentioned.
- hypochlorous acid lithium hypochlorite, potassium hypochlorite, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, strontium hypochlorite
- An example is ammonium hypochlorite.
- hypobromite and hypoiodite corresponding to these can also be used.
- halogenated isocyanuric acid or a salt thereof the general formula (III):
- A represents a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkali metal or an alkaline earth metal, and X represents the same or different, each representing a fluorine atom.
- Halogen atoms such as chlorine atom, bromine atom and iodine atom.
- the halogenated isocyanuric acid represented by the formula (1) or a salt thereof is used.
- Examples of the alkali metal that forms the halogenated isocyanurate include lithium, potassium, and sodium, and examples of the alkaline earth metal that forms the halogenated isocyanurate include calcium, magnesium, and strontium. Moreover, the salt of ammonium and halogenated isocyanuric acid is also mentioned. Moreover, these halogenated isocyanurates may form hydrates. Specific examples of the halogenated isocyanuric acid include dichloroisocyanuric acid and trichloroisocyanuric acid. Specific examples of the halogenated isocyanurate include sodium dichloroisocyanurate.
- the oxidizing agent in the step (1a) is an alkali metal hypohalite
- an alkali metal hypochlorite such as sodium hypochlorite
- the oxidizing agent is a halogenated isocyanuric acid
- sodium dichloroisocyanurate and sodium dichloroisocyanurate dihydrate are preferable because of high solubility in water and excellent bleaching and bactericidal effects in water.
- the content of the oxidizing agent is preferably about 0.03 to 10 g / L, more preferably about 1.0 to 5.0 g / L in the reaction solution.
- the content ratio of the oxidizing agent is preferably about 0.03 to 10 g / L or more, the effect of improving the hydrophilicity and bleaching effect of the cellulose fiber is obtained, and by setting it to about 10 g / L or less, polymerization is performed. The effect which suppresses a degree fall and a texture fall is acquired.
- the content of the oxidizing agent is preferably about 0.1 to 30% owf, more preferably about 3.0 to 15% owf.
- the pH of the reaction solution in step (1a) is preferably maintained at about 4 to 12, which is a pH suitable for the oxidized N-oxyl compound to act on cellulose fibers, and is maintained at about pH 8 to 11. More preferably.
- the pH of the reaction solution may be a basic substance (ammonia, potassium hydroxide, sodium hydroxide, etc.) or an acidic substance (acetic acid, oxalic acid, succinic acid, glycolic acid, malic acid, citric acid, benzoic acid and other organic acids, or It can be adjusted by appropriately adding an inorganic acid such as nitric acid, hydrochloric acid, sulfuric acid or phosphoric acid.
- a penetrant may be further added to the reaction solution used in the step (1a).
- known ones used for cellulose fibers can be applied. Specifically, anionic surfactants (carboxylates, sulfate esters, sulfonates, phosphate ester salts, etc.) Nonionic surfactants (polyethylene glycol type, other alcohol type, etc.) can be mentioned, and for example, Sintole (trade name: manufactured by Takamatsu Yushi Co., Ltd.) and the like can be used.
- the drug By adding a penetrant to the reaction solution, the drug can penetrate into the inside of the cellulose fiber, and more carboxyl groups (aldehyde groups) can be introduced to the surface of the cellulose fiber. Thereby, the hydrophilicity (hygroscopicity) of a cellulose fiber can be improved more.
- Water is used as a solvent in the reaction solution in the step (1a).
- the procedure for oxidizing the cellulose fiber is not particularly limited, but first, an N-oxyl compound and a co-catalyst are added to the reaction solvent, the cellulose fiber is further immersed, and then an oxidizing agent is added. It is preferable to add.
- an oxidizing agent is added.
- the reaction solution with respect to 1 g of cellulose fiber is preferably about 10 to 100 g, and more preferably about 15 to 30 g.
- the reaction solution is set to about 100 g or less with respect to 1 g of cellulose fiber.
- the temperature of the oxidation treatment in the step (1a) is about 0 ° C. or higher from the viewpoints that COOH groups can be sufficiently introduced into the cellulose fiber, oxidant evaporation is prevented, and effective halogen can be maintained during the oxidation treatment. Is preferable, and about 20 ° C. or higher is more preferable.
- the temperature of the oxidation treatment in the step (1a) is preferably about 50 ° C. or less, more preferably about 30 ° C. or less, from the viewpoint that the degree of polymerization of the cellulose fibers does not decrease and the embrittlement suppression of the cellulose fibers.
- the time for the oxidation treatment in the step (1a) is preferably about 1 minute or more from the viewpoint that a COOH group can be sufficiently introduced into the cellulose fiber, and the time required for the reaction cycle to begin to proceed is preferable. More than about is more preferable.
- the time for the oxidation treatment in the step (1a) is preferably about 30 minutes or less, more preferably about 15 minutes or less, from the viewpoint that the degree of polymerization of the cellulose fibers does not decrease and the embrittlement suppression of the cellulose fibers.
- Step (1b) is a step in which oxidized cellulose fibers are separated from the reaction solution, cellulose fibers and an oxidizing agent are further added to the reaction solution, and the cellulose fibers are oxidized again. That is, the step (1b) is a step of oxidizing the cellulose fiber by reusing the reaction solution used in the step (1a). Specific examples of the cellulose fiber used in the step (1b) are the same as those mentioned above.
- oxidizing agent added in the step (1b) those mentioned above are used. Specifically, a halogen acid oxidizing agent is preferable, and hypohalous acid and halogenated isocyanuric acid are used. Or these salts are more preferable. More specific oxidizing agents include alkali metal hypohalites, sodium dichloroisocyanurate and sodium dichloroisocyanurate dihydrate.
- the mixing ratio of the oxidizing agent added in the step (1b) is preferably about 0.03 to 10 g / L, more preferably about 1.0 to 5.0 g / L in the reaction solution.
- the blending ratio of the oxidizing agent is preferably about 0.03 to 30% owf, more preferably about 3.0 to 15% owf.
- the pH of the reaction solution in the step (1b) is preferably maintained at about 4 to 12, which is a pH suitable for the oxidized N-oxyl compound to act on the cellulose fibers, as in the step (1a). It is more preferable to maintain the pH at about 8-11.
- the reaction solution used in the step (1b) is out of the above pH range, the reaction solution contains a basic substance (ammonia, potassium hydroxide, sodium hydroxide, etc.) or an acidic substance (acetic acid, It can be adjusted by appropriately adding an acid, an organic acid such as succinic acid, glycolic acid, malic acid, citric acid or benzoic acid, or an inorganic acid such as nitric acid, hydrochloric acid, sulfuric acid or phosphoric acid).
- a penetrant may be further added to the reaction solution used in the oxidation treatment in the step (1b).
- the bath ratio of the reaction solution used in the step (1b) and the cellulose fiber is preferably about 10 to 100 g, more preferably about 15 to 30 g, with respect to 1 g of the cellulose fiber.
- the oxidation treatment in the above step (1b) is performed once or more, and by performing it twice or more, the oxidation reaction efficiency of the obtained cellulose fiber can be improved, which is preferable from an economical viewpoint.
- the upper limit of the number of oxidation treatment steps in the above step (1b) is not particularly limited, but 5 times or less is preferable from the viewpoint of reaction efficiency and from the viewpoint of catalyst concentration and promoter concentration management. To preferred.
- finish of the oxidation process of a process (1b) the unreacted oxidizing agent (Subhalogen acid or its salt, halogenated siasocyanuric acid or its salt, and halogenated siasocyanuric acid or its salt decompose
- Step (2) is obtained in the step (1a) and the step (1b) by oxidizing the oxidized cellulose fiber obtained in the step (1a) and the step (1b) in a reaction solution containing an oxidizing agent. It is a step of oxidizing aldehyde groups present in the obtained oxidized cellulose fiber.
- the primary hydroxyl group of the glucose unit located on the microfibril surface of the cellulose fiber is selectively oxidized to a carboxyl group.
- An aldehyde group is formed. Formation of this aldehyde group causes a beta elimination reaction or coloring during heating, leading to a decrease in strength due to the low molecular weight of the cellulose fiber.
- Step (2) is a step of oxidizing the aldehyde group produced by the steps (1a) and (1b) to a carboxyl group to obtain oxidized cellulose fibers that do not contain an aldehyde group.
- the raw material used in the step (2) is an oxidized cellulose fiber obtained by the step (1b).
- the oxidizing agent used in the step (2) is an oxidizing agent that can oxidize an aldehyde group and convert it into a carboxyl group. Specifically, halous acid or a salt thereof (chlorous acid or a salt thereof, bromous acid or a salt thereof, iodic acid or a salt thereof), a peracid (hydrogen peroxide, peracetic acid, persulfuric acid, perbenzoic acid) Acid, etc.). These oxidizing agents can be used alone or in combination of two or more. Further, it may be used in combination with an oxidase such as laccase.
- the content of the oxidizing agent can be appropriately set, but is preferably in the range of 0.01 to 50 mmol / g with respect to the cellulose fiber.
- halogen in the halite examples include chlorine, bromine and iodine.
- salt for forming the halite examples include alkali metal salts such as lithium, potassium and sodium; alkaline earth metal salts such as calcium, magnesium and strontium; ammonium salts and the like. More specific examples of the halite include lithium chlorite, potassium chlorite, sodium chlorite, calcium chlorite, magnesium chlorite, strontium chlorite, etc. An example is ammonium chlorate. In addition, bromite and iodate corresponding to these can also be used.
- a preferable oxidizing agent used in the step (2) is an alkali metal halous acid salt, and more preferably an alkali metal chlorite.
- the content of the oxidizing agent in the reaction solution is preferably about 1 to 90 g / L, more preferably about 2 to 20 g / L.
- the content ratio of the oxidizing agent is preferably about 1 to 90 g / L or more, in addition to the oxidation effect of the aldehyde group, an effect of bleaching cellulose fibers can be obtained, and by setting it to about 90 g / L or less, the oxidizing agent The effect which suppresses the embrittlement of the cellulose fiber by chlorine of this is acquired.
- the content of the oxidizing agent is preferably about 2 to 180% owf, more preferably about 4 to 40% owf.
- the pH of the reaction solution is preferably maintained in a neutral to acidic range.
- a more specific pH is preferably in the range of 3-7.
- a buffer solution it is also preferable to further add a buffer solution to the reaction solution.
- a buffer solution various buffer solutions such as a phosphate buffer solution, an acetate buffer solution, a citrate buffer solution, a borate buffer solution, a tartaric acid buffer solution, and a Tris buffer solution can be used.
- a change in pH in the reaction solution can be suppressed, and it is not necessary to continuously add acid or alkali to maintain the pH.
- the reaction solution with respect to 1 g of the cellulose fiber is preferably about 5 to 100 g, more preferably about 10 to 30 g.
- the reaction solution is set to about 100 g or less with respect to 1 g of cellulose fiber.
- a chelating agent, a surfactant, a penetrating agent, and the like may be added as appropriate in order to improve the effect of inhibiting the embrittlement of cellulose fibers by metals.
- the temperature of the oxidation treatment in the step (2) is preferably about 60 ° C. or higher from the viewpoint that the aldehyde group in the oxidized cellulose fiber can be sufficiently oxidized to a COOH acid group and the bleaching effect of the cellulose fiber can be exhibited. It is more preferable that the temperature is about ° C or higher. Further, the temperature of the oxidation treatment in the step (2) is preferably about 98 ° C. or less from the viewpoint that the degree of polymerization of the oxidized cellulose fiber does not decrease, the suppression of embrittlement of the oxidized cellulose fiber by chlorine as an oxidizing agent, and the like. It is more preferable that the temperature is not higher than about ° C.
- the time for the oxidation treatment in the step (2) is preferably about 30 minutes or more from the viewpoint that the aldehyde group in the oxidized cellulose fiber can be sufficiently oxidized to COOH acid group and the bleaching effect of the cellulose fiber can be exhibited. More than about minutes are more preferable. Further, the time for the oxidation treatment in the step (2) is preferably about 120 minutes or less from the viewpoint that the degree of polymerization of the oxidized cellulose fiber does not decrease, the suppression of embrittlement of the oxidized cellulose fiber by chlorine as an oxidizing agent, and the like. More preferably, it is less than about minutes.
- an oxidation treatment may be performed with a pressurizing device that pressurizes the inside of the reaction vessel. After completion of the oxidation treatment in the step (2), it is preferable to stop the oxidation reaction as necessary and repeat washing with water.
- Step (3) is a step of dehalogenating the oxidized cellulose fiber obtained in step (2).
- the raw material used in the dehalogenation process in the step (3) is an oxidized cellulose fiber obtained by the oxidation process in the step (2).
- a halogen-based oxidizing agent is used as the oxidizing agent in the step (1a), the step (1b), and the step (2), halogen derived from the oxidizing agent is present in the oxidized cellulose fiber after the oxidation treatment. Adhered or bonded. Therefore, it is preferable to perform a dehalogenation treatment for removing the halogen remaining on the oxidized cellulose fiber in the step (3).
- the dehalogenation treatment agent used for the dehalogenation treatment it is performed by immersing the oxidized cellulose fiber in a hydrogen peroxide solution or an ozone solution.
- the concentration of the dehalogenating agent in the reaction solution used in the dehalogenation treatment in step (3) depends on the type of the dehalogenating agent, but is preferably about 0.1 to 100 g / L in the reaction solution, About 0.67 to 10 g / L is more preferable.
- the content ratio of the dehalogenating agent is preferably about 1 to 300% owf, more preferably about 2 to 30% owf.
- the bath ratio of the reaction solution used in the dehalogenation treatment in step (3) and the cellulose fiber is preferably about 5 to 100 g, more preferably about 5 to 50 g, with respect to 1 g of cellulose fiber. preferable.
- the reaction solution is preferably about 5 to 100 g, more preferably about 5 to 50 g, with respect to 1 g of cellulose fiber. preferable.
- the pH of the reaction solution used for the dehalogenation treatment in the step (3) is preferably about 8 to 11, more preferably about 9.5 to 10.7.
- the pH of the reaction solution used for the dehalogenation treatment in the step (3) is preferably about 8 to 11, more preferably about 9.5 to 10.7.
- the temperature of the dehalogenation treatment in the step (3) is preferably about 40 ° C. or more, more preferably about 45 ° C. or more from the viewpoint of exhibiting the effect of dechlorination. Further, the temperature of the dehalogenation treatment in the step (3) is preferably about 90 ° C. or less, more preferably about 80 ° C. or less from the viewpoint of suppressing cellulose fibers due to alkalinity.
- the time for the dehalogenation treatment in the step (3) is preferably about 5 minutes or more from the viewpoint of sufficient dehalogenation treatment, and more preferably about 10 minutes or more.
- the time for the dehalogenation treatment in the step (3) is preferably about 60 minutes or less, more preferably about 40 minutes or less from the viewpoint of embrittlement and hardening of the oxidized cellulose fiber when exposed to alkaline conditions for a long time. .
- the reduction treatment in the step (4) is performed after the dehalogenation treatment in the step (3) when the dehalogenation treatment in the step (3) is performed, and the dehalogenation treatment in the step (3) is not performed. In some cases, it is preferably performed after the oxidation treatment in step (2).
- Examples of the reducing agent include those that can reduce partially generated ketone groups to alcohols, and those that do not reduce the generated carboxyl groups. Specific examples include thiourea, hydrosulfite, and bisulfite. Examples thereof include sodium, sodium borohydride, sodium cyanoborohydride, lithium borohydride and the like. Among these, sodium borohydride and sodium hydrogen sulfite are preferable from the viewpoint of excellent initial whiteness and whiteness reduction suppression.
- As the solvent in the reaction solution containing a reducing agent general water and general water such as distilled water, ion exchange water, well water, tap water, and the like are used.
- the concentration of the reducing agent contained in the reaction solution is preferably about 0.02 to 4 g / L, and more preferably about 0.2 to 2 g / L. By setting the concentration within the above range, an effect of suppressing embrittlement of the oxidized cellulose fiber due to an excessive reducing agent can be obtained.
- the content of the reducing agent is preferably about 0.06 to 12% owf, more preferably about 0.6 to 6.0% owf.
- the pH of the reaction solution when performing the reduction treatment with the reducing agent is preferably about 7 or more, more preferably about 7.5 or more, and further preferably about 8 or more, from the viewpoint of maintaining the reducing agent activity. . Further, the pH of the reaction solution when performing the reduction treatment with the reducing agent is preferably about 12 or less, more preferably about 11 or less, from the viewpoint that the embrittlement of the fabric due to the alkaline side can be suppressed.
- the pH of the reaction solution can be adjusted by appropriately adding aqueous ammonia, hydrochloric acid, soda ash, NaOH, KOH and the like.
- the reaction solution with respect to 1 g of the cellulose fiber is preferably about 5 to 100 g, and more preferably about 5 to 50 g.
- the reaction solution By setting the reaction solution to about 5 g or more with respect to 1 g of cellulose fiber, the liquid contact of the reaction solution with respect to the cellulose fiber is improved, and the effect that chlorine can be neutralized is obtained.
- the solution By setting the solution to about 50 g or less, an effect that the stirring efficiency of the cellulose fiber and the reaction solution can be maintained is obtained.
- the reaction temperature of the reduction treatment with the reducing agent is appropriately changed depending on the type and amount of the reducing agent, but is preferably about 10 to 80 ° C., and more preferably about 20 to 40 ° C.
- the type, content ratio, bath ratio, and reaction conditions of the dehalogenation treatment agent and the reducing agent are the same as those in step (3). And (4).
- the hydrophilic cellulose fiber (oxidized cellulose fiber) obtained by the above-described method for producing hydrophilic cellulose is one in which at least a part of hydroxyl groups located on the microfibril surface of cellulose are oxidized only by carboxyl groups. .
- the present invention also provides a step of oxidizing cellulose fibers in a reaction solution containing an N-oxyl compound, an oxidizing agent, and sodium sulfate to obtain oxidized cellulose fibers, and cellulose oxide from the reaction solution used in the oxidation treatment step.
- the present invention also relates to a method for reusing a reaction solution, wherein the fiber is separated, cellulose fiber and an oxidizing agent are further added to the reaction solution, and the cellulose fiber is oxidized again.
- the reaction solution used in the oxidation treatment step may be the same as the reaction solution used in the step (1a).
- reaction solution used in the oxidation treatment By reusing the reaction solution used in the oxidation treatment, it is possible to reuse the reaction solution without discarding the N-oxyl compound used as a catalyst and sodium sulfate used as a promoter. From the economical viewpoint, it is preferable. Moreover, when the cellulose fiber is further oxidized using the reused reaction solution, more carboxyl groups can be substituted than the cellulose fiber obtained in the step (1a), and the reaction efficiency is improved. The effect of doing.
- the hydrophilic cellulose fiber obtained by the method for producing a hydrophilic cellulose fiber of the present invention does not substantially contain an aldehyde group in which the carbon at the 6-position is derived from an aldehyde group even if it is subjected to heat treatment. Coloring components are difficult to produce. Therefore, the hydrophilic cellulose fiber obtained by the above production method is a material suitable for clothing use such as underwear that requires high whiteness. In addition, since quality does not deteriorate due to heat, it is a material that is easy to handle without any restrictions in processing.
- the hydrophilized cellulose fiber obtained by the above-mentioned production method has increased hygroscopicity without substantially impairing the strength of the raw material cellulose fiber because it is difficult for the cellulose microfibrils to be cut by aldehyde groups in the production process. It has become.
- the hydrophilized cellulose fiber in which the primary hydroxyl group of cellulose microfibril is oxidized to a carboxyl group can obtain a high heat dissipation effect and heat generation effect due to its high hygroscopicity, and is suitable for various fiber products.
- Such textile products include clothing articles, miscellaneous goods, interior goods, bedding goods, industrial materials, sanitary goods, and medical materials.
- the above clothing items include outing clothing, sportswear, homewear, relax wear, pajamas, sleepwear, underwear, office wear, work clothes, food lab coats, nursing lab coats, patient garments, nursing garments, student garments, kitchen garments, etc.
- Examples of the underwear include shirts, briefs, shorts, girdle, pantyhose, tights, socks, leggings, belly rolls, steteco, patches, petticoats, and the like.
- Examples of the miscellaneous goods include an apron, a towel, gloves, a muffler, a hat, shoes, a sandal, a bag, an umbrella, and the like.
- Examples of the interior goods include curtains, carpets, mats, kotatsu covers, sofa covers, cushion covers, sofa grounds, toilet seat covers, toilet seat mats, table cloths, and the like.
- Examples of the bedding article include a futon side, a blanket for blanket, a blanket, a blanket side, a pillow filler, a sheet, a waterproof sheet, a duvet cover, and a pillow cover.
- a filter etc. are mentioned as said industrial material.
- Examples of the sanitary products and medical materials include hemostatic materials, cotton, sponges, gauze, masks, bandages, supporters and the like.
- the hydrophilic cellulose fiber of the present invention can be suitably used for hemostatic materials such as hemostatic gauze.
- hemostatic materials such as hemostatic gauze.
- Such a hemostatic material can perform reliable hemostasis in a short time even for severe bleeding. Further, since the blood has solidified, after the hemostasis is completed, excess hemostatic material can be easily removed with tweezers or forceps. Furthermore, it has a sufficient hemostatic effect without causing rebleeding from the hemostatic site.
- the hydrophilic cellulose fiber of the present invention When used as a hemostatic material, examples of the fabric include knitted fabrics, woven fabrics, and nonwoven fabrics, with knitted fabrics being particularly preferred.
- the shape of the fiber can be easily maintained even when the carboxyl group is introduced at a high density by introducing the carboxyl group into the fiber.
- non-woven fabric, gauze (woven fabric), sponge, paper, etc. have strong bonds between fibers due to the effect of introduced carboxyl groups, resulting in poor rigidity and operability. Absent.
- the introduction of carboxyl groups into the fibers makes it easy to maintain the fiber shape even if the carboxyl groups are introduced at high density.
- TEMPO 2,2,6,6-tetramethylpiperidine-N-oxyl
- hypochlorous acid of the dough cellulose fiber
- TEMPO and bow glass shown in Table 1 were dissolved in water, and the dough was sufficiently immersed in the resulting solution.
- a 5% by weight NaClO aqueous solution was further added to the solution in which the dough was immersed, and the pH was adjusted to 1.0 M with an aqueous HCl solution of 1.0 M. Under the conditions shown in Table 1, 1.0 M was added.
- An oxidation treatment was carried out for 10 minutes while adjusting the pH with an aqueous NaOH solution.
- step (2) After performing the oxidation treatment of step (2) according to the reaction solution and reaction conditions shown in Table 1, the sample was taken out, washed with hot water at 60 ° C., and further washed with water.
- Table 2 shows the carboxyl group amount (COOH group amount), the degree of polymerization, and the reaction efficiency for each sample dough (Examples 1 to 5) manufactured by the above manufacturing process.
- the amount of carboxyl groups was measured by conductometric titration.
- the degree of polymerization was measured by the following method.
- the fibers collected from each of the sample fabrics were reduced with sodium borohydride in advance to reduce residual aldehyde groups to alcohol, and this was dissolved in a 0.5 M copper ethylenediamine solution, and the degree of polymerization was determined by a viscosity method. .
- the copper ethylenediamine solution is alkaline, and if aldehyde groups remain in the oxidized cellulose, a beta elimination reaction may occur in the dissolution process and the molecular weight may decrease.
- the aldehyde group was converted to an alcoholic hydroxyl group.
- the formula for calculating the degree of polymerization of cellulose from the viscosity of cellulose dissolved in 0.5 M copper ethylenediamine solution is “Isogai, A., Mutoh, N., Onabe, F., Usuda, M.,“ Vis cosity “Measurements of cellulose / SO 2 -amine-dimethylsulfoxide solution”, Seni Gakkaishi, 45, 299-306 (1989). ” Furthermore, the reaction efficiency indicates the reaction rate of the COOH group amount of each Example when the reaction rate of the COOH group amount of Example 1 is 100%.
- “Generation” shown in Table 2 indicates the 40th cotton yarn milled cotton fabric after scouring, and “Blanked cotton fabric” indicates the 40th cotton yarn milled cotton fabric after scouring, and then treated with NaClO 2. And H 2 O 2 bleached, dehydrated and dried cotton cloth.
- Table 4 shows the carboxyl group amount (COOH group amount), the degree of polymerization, and the reaction efficiency for each sample fabric (Comparative Examples 1 to 5) manufactured by the above manufacturing process.
- the carboxyl group amount was measured by the same method as described above for the degree of polymerization and the reaction efficiency.
- “Formed” shown in Table 4 indicates the 40th cotton yarn milled fabric after scouring
- “Blanked cotton fabric” indicates the 40th cotton milled fabric after scouring, followed by NaClO 2 treatment and H It is a cotton cloth that has been bleached, dehydrated and dried by 2 O 2 treatment. Furthermore, about the sample obtained in Example 1 and Comparative Example 1, distribution of the carboxyl group of a fiber cross section was confirmed.
- the sample was immersed in ion-exchanged water, adjusted to pH 3 with 1N-HCl, treated at 25 ° C. for 3 hours, and then thoroughly washed with distilled water. Thereafter, lead acetate (II) trihydrate was added in an amount 60 times the carboxyl group contained in the sample, treated at 25 ° C. for 6 hours, washed with water and dried.
- the Pb distribution of the fiber cross section was measured using SEM-EDX (JSM-6390LA: manufactured by JEOL Ltd.). 3 is a photomicrograph of the fiber cross section of the sample obtained in Example 1, and FIG. 4 is a photo showing the Pb distribution of the fiber cross section of the sample obtained in Example 1.
- FIG. 5 is a micrograph of the fiber cross section of the sample obtained in Comparative Example 1
- FIG. 6 is a photograph showing the Pb distribution of the fiber cross section of the sample obtained in Comparative Example 1. 4 and 6, each color shown in the lower left represents the Pb density, and the higher the color shown in the upper part, the higher the Pb density. From the results of FIGS. 4 and 6, it can be seen that the sample obtained in Example 1 has a higher Pb concentration inside the fiber than the sample obtained in Comparative Example 1.
- FIG. 1 a graph plotting the relationship between the number of tests in the oxidation treatment step and the reaction efficiency is shown in FIG.
- the horizontal axis represents the number of oxidation treatment tests
- the vertical axis represents the reaction efficiency. 1 is a plot when bow glass is used as the promoter
- ⁇ is a plot when NaBr is used as the promoter.
- Example 6 The dough (cellulose fiber) was subjected to an oxidation treatment with TEMPO and sodium dichloroisocyanurate (SDIC) in the same procedure as in Example 1 with the reaction solutions and reaction conditions shown in Table 5. Thereafter, samples were obtained by the same method as in Example 1.
- “produced” shown in Table 6 indicates the 40th cotton yarn milled fabric after scouring, and “bleached cotton fabric” indicates that after the 40th cotton milled fabric is scoured, NaClO 2 treatment and H It is a cotton cloth that has been bleached, dehydrated and dried by 2 O 2 treatment.
- Example 1 using NaClO was also performed when the cellulose fiber was oxidized using TEMPO and SDIC using sodium sulfate (bow glass) as a co-catalyst in step (1a). As in ⁇ 5, the reaction efficiency increased as the number of times the reaction solution was reused increased. Therefore, when reusing the reaction solution used at the process (1a), it turned out that it is also effective to use SDIC as an oxidizing agent.
- Example 13 With the use solutions and reaction conditions shown in Table 8, 100% cotton knitted fabric (40th cotton yarn milled cotton fabric) was mercerized. Using the obtained mercerized cotton fabric, steps (1a), (2), and (3) were performed in the same manner as in the procedure of Example 1, with the reaction solutions and reaction conditions shown in Table 8. In the subsequent steps, a sample was obtained by the same method as in Example 1.
- Example 14 A sample was obtained in the same manner as in Example 13 except that the reaction time was 4 hours in the step (1a).
- the present invention it is possible to provide a method for producing hydrophilic cellulose fibers by oxidizing a part of hydroxyl groups of cellulose fibers to carboxyl groups. Moreover, according to this invention, the hemostatic material which has the outstanding hemostatic effect can be provided.
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Abstract
Description
以上の知見に基づき、本発明は、N-オキシル化合物、酸化剤、及び助触媒を含む反応溶液中で、セルロース繊維を酸化させ、更に当該反応溶液を再利用してセルロース繊維を酸化させる親水性化セルロース繊維の製造方法を提供することを目的とする。
を含む親水性化セルロース繊維の製造方法。
項2.工程(1a)で用いられるN-オキシル化合物が2,2,6,6-テトラメチルピペリジン-N-オキシルである項1に記載の親水性化セルロース繊維の製造方法。
項3.工程(1a)で用いられるセルロース繊維がレーヨンである項1又は2に記載の親水性化セルロース繊維の製造方法。
項4.工程(1b)を2回以上行う、項1に記載の親水性化セルロース繊維の製造方法。
項5.工程(1a)及び/又は工程(1b)で用いられる酸化剤がハロゲン酸系酸化剤である項1又は2に記載の親水性化セルロース繊維の製造方法。
項6.工程(1a)及び/又は工程(1b)で用いられるハロゲン酸系酸化剤が、次亜ハロゲン酸、ハロゲン化イソシアヌル酸又はこれらの塩である項3に記載の親水性化セルロース繊維の製造方法。
項7.(2)工程(1a)及び工程(1b)で得られた酸化セルロース繊維を、酸化剤を含む反応溶液中で酸化させる工程
をさらに含む項1~4のいずれかに記載の親水性化セルロース繊維の製造方法。
項8.工程(2)で用いられる酸化剤が、ハロゲン酸系酸化剤である項5に記載の親水性化セルロース繊維の製造方法。
項9.工程(2)で用いられるハロゲン酸系酸化剤が、亜ハロゲン酸又はその塩である項6に記載の親水性化セルロース繊維の製造方法。
項10.(3)工程(2)で得られた酸化セルロース繊維を、脱ハロゲン化剤で脱ハロゲン処理する工程
をさらに含む項5~7のいずれかに記載の親水性化セルロース繊維の製造方法。
項11.(4a)工程(2)によって得られた酸化セルロース繊維を、還元剤を含む反応溶液中で還元させる還元処理工程
をさらに含む項5~7のいずれかに記載の親水性化セルロース繊維の製造方法。
項12.(4b)工程(3)によって得られた酸化セルロース繊維を、還元剤を含む反応溶液中で還元させる還元処理工程
をさらに含む項8に記載の親水性化セルロース繊維の製造方法。
項13.工程(2)で得られた酸化セルロース繊維を、脱ハロゲン化剤、及び還元剤と混合し、酸化セルロース繊維中に残存するハロゲンを除去する脱ハロゲン処理を行うと共に、酸化セルロース繊維のグルコース単位の2位及び/又は3位に存在するケトン基を還元する還元処理を行う工程
をさらに含む項5~7のいずれかに記載の親水性化セルロース繊維の製造方法。
項14.脱ハロゲン化剤が、過酸化水素、及びオゾンよりなる群から選ばれる少なくとも1種である項8又は11に記載の親水性化セルロース繊維の製造方法。
項15.還元剤が、チオ尿素、ハイドロサルファイト、亜硫酸水素ナトリウム、水素化ホウ素ナトリウム、シアノ水素化ホウ素ナトリウム、及び水素化ホウ素リチウムよりなる群から選ばれる少なくとも1種である項9~12のいずれかに記載の親水性化セルロース繊維の製造方法。
項16.N-オキシル化合物、酸化剤、及び硫酸ナトリウムを含む反応溶液中で、セルロース繊維を酸化させ、酸化セルロース繊維を得る工程、及び前記酸化処理工程で使用した反応溶液から酸化セルロース繊維を分離し、前記反応溶液中にセルロース繊維及び酸化剤をさらに添加し、再度セルロース繊維を酸化させることを特徴とする、反応溶液を再利用する方法。
項17.項1~15のいずれかに記載の親水性化セルロース繊維の製造方法を用いて得られることを特徴とする親水性化セルロース繊維。
項18.項17に記載の親水性化セルロース繊維を用いて得られる止血材料。
また、前記酸化工程で使用した反応溶液を再利用することによって、触媒として使用されるN-オキシル化合物、及び助触媒として使用される硫酸ナトリウムを廃棄することなく反応溶液を再利用することが可能であり、経済的観点からも有用である。
工程(1a)は、N-オキシル化合物、酸化剤、及び硫酸ナトリウムを含む反応溶液中で、セルロース繊維を酸化させる工程、即ち、セルロース繊維中の6位にCOOH基を導入させた酸化セルロース繊維を得る工程である。
上記レーヨンとしては、例えば、ビスコースレーヨン、銅アンモニアレーヨン、ポリノジックレーヨン等を挙げることができる。
なお、原料セルロース繊維の形態としては、織編物や不織布等の布帛に限らず、フィラメント、ステープル、紐等の糸状物であってもよい。また、繊維の構造組織としては、混繊、混紡、混織、交織、交編したものであってもよい。
本発明では、工程(1a)の酸化処理において、反応溶液中に助触媒として硫酸ナトリウムを含有させることにより、副生される塩による反応効率の低下を抑制することができ、後述の工程(1b)の酸化処理による反応溶液の再利用が可能となる。
なお、硫酸ナトリウムの含有割合と、セルロース繊維へのCOOH基の導入量との関係の一例を図2に示す。
ここで、単位「%owf」とは、繊維重量に対する重量%を表し、以下同じ意味である。
式(II):
等が挙げられる。
また、前記TEMPO誘導体の具体例としては、4-アセトアミドTEMPO、4-カルボキシTEMPO、4-フォスフォノオキシTEMPO、4-アミノ-TEMPO、4-(2-ブロモアセトアミド)-TEMPO、4-ヒドロキシTEMPO、4-オキシTEMPO、4-メトキシTEMPO等が挙げられる。
これらのN-オキシル化合物において、TEMPO、4-メトキシTEMPO及び4-アセトアミドTEMPOは、セルロース繊維のグルコース単位の6位の炭素を酸化させる反応速度が大きいため、好ましい。
また、反応溶液中のN-オキシル化合物の含有割合は、0.03~9.0%owf程度が好ましく、0.75~6.0%owf程度がより好ましい。
次亜ハロゲン酸におけるハロゲンとしては、塩素、臭素、ヨウ素が挙げられ、次亜ハロゲン酸の具体例としては、次亜塩素酸、次亜臭素酸、次亜ヨウ素酸が挙げられる。
次亜ハロゲン酸塩を形成する金属塩としては、リチウム、カリウム、ナトリウム等のアルカリ金属塩;カルシウム、マグネシウム、ストロンチウム等のアルカリ土類金属塩等が挙げられる。また、アンモニウムと次亜ハロゲン酸との塩も挙げられる。
で表されるハロゲン化イソシアヌル酸又はその塩が用いられる。
ハロゲン化イソシアヌル酸の具体例としては、ジクロロイソシアヌル酸、トリクロロイソシアヌル酸等が挙げられる。また、ハロゲン化イソシアヌル酸塩の具体例としては、ジクロロイソシアヌル酸ナトリウム等が挙げられる。
また、酸化剤の含有割合は、0.1~30%owf程度が好ましく、3.0~15%owf程度がより好ましい。
反応溶液のpHは、塩基性物質(アンモニア、水酸化カリウム、水酸化ナトリウム等)又は酸性物質(酢酸、シュウ酸、コハク酸、グリコール酸、リンゴ酸、クエン酸、安息香酸等の有機酸、あるいは硝酸、塩酸、硫酸、リン酸等の無機酸)を適宜添加することで調整することができる。
工程(1a)の反応溶液における溶媒としては、水が用いられる。
工程(1b)は、反応溶液から酸化セルロース繊維を分離し、当該反応溶液にセルロース繊維、及び酸化剤をさらに添加し、再度セルロース繊維を酸化させる工程である。
即ち、工程(1b)は、工程(1a)で用いた反応溶液を再利用して、セルロース繊維を酸化させる工程である。
工程(1b)で用いるセルロース繊維の具体例としては、前記で挙げられたものと同様のものが用いられる。
また、酸化剤の配合割合は、0.1~30%owf程度が好ましく、3.0~15%owf程度がより好ましい。
工程(1b)で用いられる反応溶液が、上記のpHの範囲から外れている場合には、反応溶液に、塩基性物質(アンモニア、水酸化カリウム、水酸化ナトリウム等)又は酸性物質(酢酸、シュウ酸、コハク酸、グリコール酸、リンゴ酸、クエン酸、安息香酸等の有機酸、あるいは硝酸、塩酸、硫酸、リン酸等の無機酸)を適宜添加することで調整することができる。
工程(1b)で用いられる反応溶液とセルロース繊維との浴比としては、セルロース繊維1gに対する反応溶液が、10~100g程度であることが好ましく、15~30g程度であることがより好ましい。セルロース繊維1gに対して反応溶液を10g程度以上に設定することにより、セルロース繊維と反応溶液の接触効率が良好になるという効果が得られ、セルロース繊維1gに対して反応溶液を100g程度以下に設定することにより、セルロース繊維と反応溶液の接触効率を保持できるという効果が得られる。
工程(1b)における反応溶媒、酸化処理の温度、及び時間としては、前記の工程(1a)と同程度である。
なお、上記の工程(1b)の酸化処理の工程の回数の上限は、特に限定されるものではないが、5回以下が、反応効率の観点から、また、触媒濃度、助触媒濃度管理の観点から好ましい。
なお、工程(1b)の酸化処理の終了後は、必要に応じて未反応の酸化剤(次ハロゲン酸又はその塩、ハロゲン化シソシアヌル酸又はその塩、及びハロゲン化シソシアヌル酸又はその塩が分解した次ハロゲン酸又はその塩等)を除去する処理を行い、その後、水洗を繰り返すことが好ましい。
工程(2)は、前記工程(1a)及び工程(1b)で得られた酸化セルロース繊維を、酸化剤を含む反応溶液中で酸化させることにより、前記工程(1a)及び工程(1b)で得られた酸化セルロース繊維中に存在するアルデヒド基を酸化する工程である。
前記工程(1a)及び工程(1b)の酸化処理によって、セルロース繊維のミクロフィブリル表面に位置するグルコース単位の1級水酸基が選択的にカルボキシル基へと酸化されるが、カルボキシル基以外にも一部アルデヒド基が形成される。このアルデヒド基の形成によってベータ脱離反応や加熱時の着色が引き起こされ、セルロース繊維の低分子化による強度低下を招いてしまう。
工程(2)は、前記工程(1a)及び工程(1b)によって生成されたアルデヒド基をカルボキシル基に酸化させ、アルデヒド基を含まない酸化セルロース繊維を得る工程である。
工程(2)で用いられる酸化剤は、アルデヒド基を酸化してカルボキシル基に変換することができる酸化剤である。具体的には、亜ハロゲン酸又はその塩(亜塩素酸又はその塩、亜臭素酸又はその塩、亜ヨウ素酸又はその塩等)、過酸(過酸化水素、過酢酸、過硫酸、過安息香酸等)が含まれる。これらの酸化剤は単独又は2種以上の組み合わせで使用することができる。また、ラッカーゼ等の酸化酵素と組み合わせて用いてもよい。酸化剤の含有量は適宜に設定することができるが、セルロース繊維に対して0.01~50mmol/gの範囲とすることが好ましい。
酸化剤の含有割合は、反応溶液中、1~90g/L程度が好ましく、2~20g/L程度がより好ましい。酸化剤の含有割合を、1g/L程度以上に設定することによって、アルデヒド基の酸化効果に加えて、セルロース繊維を漂白する効果が得られ、90g/L程度以下に設定することによって、酸化剤の塩素によるセルロース繊維の脆化を抑止する効果が得られる。
また、酸化剤の含有割合は、2~180%owf程度が好ましく、4~40%owf程度がより好ましい。
前記緩衝液を用いることによって、反応溶液中のpHの変化を抑えることができ、pHを維持するための酸やアルカリの連続的な添加が不要となる。
工程(2)の酸化処理において、金属類によるセルロース繊維の脆化抑止効果を向上させるために、さらに、キレート剤、界面活性剤、浸透剤等を適宜添加してもよい。
なお、工程(2)の酸化処理では、反応容器を密閉することが可能であることから、反応容器の内部を加圧する加圧装置を併設し、酸化処理してもよい。
工程(2)の酸化処理終了後は、必要に応じて酸化反応を停止させ、水洗を繰り返すことが好ましい。
工程(3)は、前記工程(2)で得られた酸化セルロース繊維を脱ハロゲン処理する工程である。
工程(3)の脱ハロゲン処理で用いられる原料は、前記工程(2)の酸化処理によって得られた酸化セルロース繊維である。
前記工程(1a)及び工程(1b)、並びに工程(2)において、酸化剤としてハロゲン系酸化剤が用いられた場合、酸化処理の後の酸化セルロース繊維には、前記酸化剤に由来するハロゲンが付着あるいは結合している。
そのため、工程(3)で、このような酸化セルロース繊維に残留したハロゲンを除去する脱ハロゲン処理を行うことが好ましい。脱ハロゲン処理に用いられる脱ハロゲン処理剤としては、過酸化水素溶液やオゾン溶液に酸化セルロース繊維を浸漬することで行う。
また、脱ハロゲン処理剤の含有割合は、1~300%owf程度が好ましく、2~30%owf程度がより好ましい。
前記工程(1a)、工程(1b)、工程(2)、及び工程(3)の脱ハロゲン処理によって、セルロース繊維により多くのカルボキシル基をセルロース繊維表面に導入することができるが、前記酸化処理によって、さらに黄変(白度低下)する場合がある。これは、セルロース繊維の6位の炭素のカルボキシル化だけでなく、2位や3位の炭素も一部酸化され、ケトンが生成されるためであると考えられる。そのため、前記工程の後に、さらに、還元剤による還元処理を行うことによって、生成したケトンを還元し、親水性化セルロース繊維の黄変(白度低下)を抑制することができる。
なお、工程(4)の還元処理は、工程(3)の脱ハロゲン処理を行う場合には、工程(3)の脱ハロゲン処理を行った後に行い、工程(3)の脱ハロゲン処理を行わない場合には、工程(2)の酸化処理後に行われることが好ましい。
還元剤を含む反応溶液における溶媒としては、蒸留水、イオン交換水、井戸水、水道水等、一般的な水及び水全般が用いられる。反応溶液に含まれる還元剤の濃度は、0.02~4g/L程度が好ましく、0.2~2g/L程度がより好ましい。前記範囲の濃度に設定することにより、過剰な還元剤による酸化セルロース繊維の脆化を抑えるという効果が得られる。
また、還元剤の含有割合は、0.06~12%owf程度が好ましく、0.6~6.0%owf程度がより好ましい。
なお、前記の工程(3)の脱ハロゲン化処理、及び工程(4)の還元処理は、同時に行ってもよい。
工程(3)の脱ハロゲン化処理、及び工程(4)の還元処理を同時に行う場合の脱ハロゲン処理剤及び還元剤の種類、含有割合、浴比、並びに反応条件は、前記の工程(3)及び(4)と同様である。
また、本発明は、N-オキシル化合物、酸化剤、及び硫酸ナトリウムを含む反応溶液中で、セルロース繊維を酸化させ、酸化セルロース繊維を得る工程、及び前記酸化処理工程で使用した反応溶液から酸化セルロース繊維を分離し、前記反応溶液中にセルロース繊維及び酸化剤をさらに添加し、再度セルロース繊維を酸化させることを特徴とする、反応溶液を再利用する方法にも関する。
前記酸化処理工程で用いられる反応溶液は、前記の工程(1a)で用いた反応溶液と同様のものが挙げられる。
また、再利用した反応溶液を用いて、さらに、セルロース繊維に酸化処理を行った場合、工程(1a)で得られるセルロース繊維よりもより多くのカルボキシル基を置換させることができ、反応効率が向上するという効果を奏する。
さらに、上記の製造方法によって得られる親水性化セルロース繊維は、その製造工程において、アルデヒド基によるセルロースミクロフィブリルの切断が生じ難いため、原料セルロース繊維の強度をほとんど損なわずに吸湿性を高めたものとなっている。
かかる繊維製品としては、例えば、衣料用品、雑貨用品、インテリア用品、寝具用品、産業用資材、衛生用品、医療材料等が挙げられる。
上記衣料用品としては、外出着衣料、スポーツウェア、ホームウェア、リラックスウェア、パジャマ、寝間着、肌着、オフィスウェア、作業服、食品白衣、看護白衣、患者衣、介護衣、学生服、厨房衣等が挙げられ、肌着としては、例えばシャツ、ブリーフ、ショーツ、ガードル、パンティストッキング、タイツ、ソックス、レギンス、腹巻き、ステテコ、パッチ、ペチコート等が挙げられる。
上記雑貨用品としては、エプロン、タオル、手袋、マフラー、帽子、靴、サンダル、かばん、傘等が挙げられる。
上記インテリア用品としては、カーテン、じゅうたん、マット、こたつカバー、ソファーカバー、クッションカバー、ソファー用側地、便座カバー、便座マット、テーブルクロス等が挙げられる。
上記寝具用品としては、布団用側地、布団用詰めわた、毛布、毛布用側地、枕の充填材、シーツ、防水シーツ、布団カバー、枕カバー等が挙げられる。
上記産業用資材としては、フィルター等が挙げられる。
上記衛生用品、医療材料としては、止血材料、コットン、スポンジ、ガーゼ、マスク、包帯、サポーター等が挙げられる。
このような止血材料は、激しい出血に対しても短時間で確実な止血を行うことができる。また、血液が固まることで、止血完了後、ピンセットや鉗子等で容易に剰余の止血材料を除去することができる。更に、止血部位から、再出血をおこさず充分な止血効果を有する。
本発明の親水性化セルロース繊維を編物とした場合、繊維内部までカルボキシル基が導入されることで、高密度でカルボキシル基を導入しても繊維形状を保持しやすい。また、不織布やガーゼ(織地)、スポンジ、紙等では導入されたカルボキシル基の影響により繊維間同士の結合が強く剛度が高くなり操作性が悪くなるが、編物とした場合はそのような不具合がない。
更に、伸縮性に優れる編地を用いることで、伸張状態で加工処理を行なうことができ、しなやかで密着性のよい止血材料が得られ、操作性の向上が可能である。生地が不織布やガーゼ(織地)である場合と比較して、繊維内部までカルボキシル基が導入されることで、高密度でカルボキシル基を導入しても繊維形状を保持しやすくなる。
・工程(1a)
表1に示す反応溶液及び反応条件で、以下の手順で生地(セルロース繊維)の2,2,6,6-テトラメチルピペリジン-N-オキシル(以下、TEMPOとも表記する)、及び次亜塩素酸ナトリウム(NaClO)による酸化処理を行った。なお、生地としては、綿100%編生地(40番手の綿糸フライス生成り生地)を用いた。
前記工程(1a)の酸化処理後、水洗したサンプル生地を、さらに表1に示す反応溶液及び反応条件で、亜塩素酸ナトリウム(NaClO2)による酸化処理を行った。なお、表1中のCG1000は、亜塩素漂白用キレート剤(ネオクリスタル(日華化学社製))であり、NaClO2は、25重量%の水溶液を用いた。
前記、工程(2)の酸化処理後、湯洗い、及び水洗を行ったサンプル生地を、さらに表1に示す条件の反応溶液で過酸化水素(H2O2)による脱塩素処理を行った。なお、表1中のPLC7000は、ポリカルボン酸系キレート剤(ネオレート(日華化学社製))であり、H2O2は、35重量%の水溶液を用いた。
前記、脱塩素処理後、湯洗い、及び水洗を行ったサンプル生地を、さらに表1に示す条件の反応溶液で還元処理を行った。
前記還元工程を行った後、サンプルを取り出し、水洗した。
前記還元処理(工程(4))後のサンプル生地を、pHが4になるように10%酢酸水溶液を用いて中和処理を行った。
前記中和処理が終了したサンプル生地を、水洗い(5分間×2回)を行った。その後、サンプル生地を40℃の乾燥室で乾燥させた。
実施例1の工程(1a)と同様の処理を行い、工程(1a)の酸化処理後、生地(セルロース繊維)を取り出し、使用後の反応溶液に、さらに5重量%のNaClO水溶液を135%owf(45g/L)添加し、さらに別の生地(セルロース繊維)(綿100%編生地(40番手の綿糸フライス生成り生地))を入れ、浴比(生地:反応溶液=1:30(重量比))にて、実施例1の工程(1a)と同様の反応条件にて、酸化処理を行った(工程(1b))。
それ以降の工程は、実施例1と同様の方法によってサンプルを得た。
実施例2の工程(1a)及び工程(1b)の酸化処理と同様の処理を行い、工程(1b)の酸化処理後、生地(セルロース繊維)を取り出し、使用後の反応溶液に、さらに5重量%のNaClO水溶液を135%owf(45g/L)添加し、さらに別の生地(セルロース繊維)(綿100%編生地(40番手の綿糸フライス生成り生地))を入れ、浴比(生地:反応溶液=1:30(重量比))にて、実施例1の工程(1a)と同様の反応条件にて、酸化処理を行った。
それ以降の工程は、実施例1と同様の方法によってサンプルを得た。
実施例3の酸化処理と同様の処理を行い、酸化処理後、生地(セルロース繊維)を取り出し、使用後の反応溶液に、さらに5重量%のNaClO水溶液を135%owf(45g/L)添加し、さらに別の生地(セルロース繊維)(綿100%編生地(40番手の綿糸フライス生成り生地))を入れ、浴比(生地:反応溶液=1:30(重量比))にて、実施例1の工程(1a)と同様の反応条件にて、酸化処理を行った。
それ以降の工程は、実施例1と同様の方法によってサンプルを得た。
実施例4の酸化処理と同様の処理を行い、酸化処理後、生地(セルロース繊維)を取り出し、使用後の反応溶液に、さらに5重量%のNaClO水溶液を135%owf(45g/L)添加し、さらに別の生地(セルロース繊維)(綿100%編生地(40番手の綿糸フライス生成り生地))を入れ、浴比(生地:反応溶液=1:30(重量比))にて、実施例1の工程(1a)と同様の反応条件にて、酸化処理を行った。
それ以降の工程は、実施例1と同様の方法によってサンプルを得た。
表2に、上記の製造工程によって製造された各サンプル生地(実施例1~5)についてのカルボキシル基量(COOH基量)、重合度、及び反応効率を示す。
なお、カルボキシル基量は、電導度滴定により測定した。
また、重合度は以下の方法により測定した。
銅エチレンジアミン溶液はアルカリ性であり、酸化セルロース中にアルデヒド基が残存していた場合には、溶解過程でベータ脱離反応が起こって分子量が低下してしまう可能性があるため、予め還元処理してアルデヒド基をアルコール性水酸基に変換した。
0.5Mの銅エチレンジアミン溶液に溶解させたセルロースの粘度から、セルロースの重合度を求める式については、「Isogai, A., Mutoh, N., Onabe, F., Usuda, M., “Vis cosity measurements of cellulose/SO2-amine- dimethylsulfoxide solution”, Seni Gakkaishi, 45, 299-306 (1989). 」を参考にした。
さらに、反応効率は、実施例1のCOOH基量の反応率を100%としたときの各実施例のCOOH基量の反応割合を示したものである。
また、表2に示す「生成り」は、精練後の40番手の綿糸フライス生成り綿生地を示し、「漂白後綿布」は、40番手の綿糸フライス生成り綿生地を精練後、NaClO2処理とH2O2処理にて漂白し、脱水、乾燥させた綿布である。
表3に示す反応溶液及び反応条件で、実施例1の手順と同様の方法で生地(セルロース繊維)のTEMPO及びNaClOによる酸化処理を行った。
それ以降の工程は、実施例1と同様の方法によってサンプルを得た。
比較例1の工程(1a)の酸化処理と同様の処理を行い、工程(1a)の酸化処理後、生地(セルロース繊維)を取り出し、使用後の反応溶液に、さらに5重量%のNaClO水溶液を115%owf(38g/L)添加し、さらに別の生地(セルロース繊維)(綿100%編生地(40番手の綿糸フライス生成り生地))を入れ、浴比(生地:反応溶液=1:30(重量比))にて、比較例1の工程(1a)と同様の反応条件にて、酸化処理を行った(工程(1b))。
それ以降の工程は、比較例1と同様の方法によってサンプルを得た。
比較例2の工程(1a)及び工程(1b)の酸化処理と同様の処理を行い、工程(1b)の酸化処理後、生地(セルロース繊維)を取り出し、使用後の反応溶液に、さらに5重量%のNaClO水溶液を115%owf(38g/L)添加し、さらに別の生地(セルロース繊維)(綿100%編生地(40番手の綿糸フライス生成り生地))を入れ、浴比(生地:反応溶液=1:30(重量比))にて、比較例1の工程(1a)と同様の反応条件にて、酸化処理を行った。
それ以降の工程は、比較例1と同様の方法によってサンプルを得た。
比較例3の酸化処理と同様の処理を行い、酸化処理後、生地(セルロース繊維)を取り出し、使用後の反応溶液に、さらに5重量%のNaClO水溶液を115%owf(38g/L)添加し、さらに別の生地(セルロース繊維)(綿100%編生地(40番手の綿糸フライス生成り生地))を入れ、浴比(生地:反応溶液=1:30(重量比))にて、比較例1の工程(1a)と同様の反応条件にて、酸化処理を行った。
それ以降の工程は、比較例1と同様の方法によってサンプルを得た。
比較例4の酸化処理と同様の処理を行い、酸化処理後、生地(セルロース繊維)を取り出し、使用後の反応溶液に、さらに5重量%のNaClO水溶液を115%owf(38g/L)添加し、さらに別の生地(セルロース繊維)(綿100%編生地(40番手の綿糸フライス生成り生地))を入れ、浴比(生地:反応溶液=1:30(重量比))にて、比較例1の工程(1a)と同様の反応条件にて、酸化処理を行った。
それ以降の工程は、比較例1と同様の方法によってサンプルを得た。
表4に、上記の製造工程によって製造された各サンプル生地(比較例1~5)についてのカルボキシル基量(COOH基量)、重合度、及び反応効率を示す。
なお、カルボキシル基量は、重合度、及び反応効率は前記と同じ方法で測定した。
また、表4に示す「生成り」は、精練後の40番手の綿糸フライス生成り生地を示し、「漂白後綿布」は、40番手の綿糸フライス生成り生地を精練後、NaClO2処理とH2O2処理にて漂白し、脱水、乾燥させた綿布である。
更に、実施例1及び比較例1で得られたサンプルについて、繊維断面のカルボキシル基の分布を確認した。具体的には、イオン交換水にサンプルを浸漬し、1N-HClでpH3に調整後25℃で3時間処理した後、蒸留水で充分に洗浄した。その後、酢酸鉛(II)三水和物を試料に含まれるカルボキシル基の60倍量添加し、25℃で6時間処理して水洗、乾燥した。そして、繊維断面のPb分布をSEM-EDX(JSM-6390LA:日本電子社製)を用いて測定した。なお、図3は実施例1で得られたサンプルの繊維断面の顕微鏡写真であり、図4は実施例1で得られたサンプルの繊維断面のPb分布を示す写真である。また、図5は比較例1で得られたサンプルの繊維断面の顕微鏡写真であり、図6は比較例1で得られたサンプルの繊維断面のPb分布を示す写真である。
図4及び図6において、左下に示した各色はPbの濃度を表し、上部に示した色であるほど、Pbの濃度が高い。
図4及び図6の結果から、実施例1で得られたサンプルでは、比較例1で得られたサンプルと比較して、繊維内部におけるPb濃度が高くなっていることがわかる。
表4及び図1より、TEMPO、及びNaClOによるセルロース繊維の酸化処理で、工程(1a)で助触媒としてNaBrを用いた比較例1~5では、反応溶液の再利用の回数が増えるに従い、反応効率が減少した。
これは、酸化処理においてNaClOの消費により副生されるNaClが、助触媒であるNaBrの反応を阻害したものであると考えられる。さらに、反応溶液の再利用の回数ごとに、逐次NaClOを添加しているため、それに伴い、NaClの副生される量も増大し、TEMPO酸化の反応阻害がより顕著に現れたものと考えられる。
これは、助触媒として添加したが、副生成物であるNaClによって反応の阻害を受けなかったため、セルロース繊維の酸化処理が円滑に行われたものと考えられる。また、助触媒として硫酸ナトリウム(ボウ硝)を用いることによって、副生成物であるNaClによる反応阻害の影響が実質的に生じないため、反応溶液の再利用の回数ごとに逐次添加したNaClOにより、効率よくセルロース繊維のヒドロキシル基をカルボキシル基に酸化させることができた。その結果として、セルロース繊維の反応効率が増加したものと考えられる。
表5に示す反応溶液及び反応条件で、実施例1と同様の手順で生地(セルロース繊維)のTEMPO、及びジクロロイソシアヌル酸ナトリウム(SDIC)による酸化処理を行った。それ以降は、実施例1と同様の方法によってサンプルを得た。
実施例6の工程(1a)の酸化処理と同様の処理を行い、工程(1a)の酸化処理後、生地(セルロース繊維)を取り出し、使用後の反応溶液に、さらにSDICを10%owf(3.3g/L)添加し、さらに別の生地(セルロース繊維)(綿100%編生地(40番手の綿糸フライス生成り生地))を入れ、浴比(生地:反応溶液=1:30(重量比))にて、実施例6の工程(1a)と同様の反応条件にて、酸化処理を行った(工程(1b))。
それ以降の工程は、実施例6と同様の方法によってサンプルを得た。
実施例7の工程(1a)及び工程(1b)の酸化処理と同様の処理を行い、工程(1b)の酸化処理後、生地(セルロース繊維)を取り出し、使用後の反応溶液に、さらにSDICを10%owf(3.3g/L)添加し、さらに別の生地(セルロース繊維)(綿100%編生地(40番手の綿糸フライス生成り生地))を入れ、浴比(生地:反応溶液=1:30(重量比))にて、実施例6の工程(1a)と同様の反応条件にて、酸化処理を行った。
それ以降の工程は、実施例6と同様の方法によってサンプルを得た。
実施例8の酸化処理と同様の処理を行い、酸化処理後、生地(セルロース繊維)を取り出し、使用後の反応溶液に、さらにSDICを10%owf(3.3g/L)添加し、さらに別の生地(セルロース繊維)(綿100%編生地(40番手の綿糸フライス生成り生地))を入れ、浴比(生地:反応溶液=1:30(重量比))にて、実施例6の工程(1a)と同様の反応条件にて、酸化処理を行った。
それ以降の工程は、実施例6と同様の方法によってサンプルを得た。
実施例9の酸化処理と同様の処理を行い、酸化処理後、生地(セルロース繊維)を取り出し、使用後の反応溶液に、さらにSDICを10%owf(3.3g/L)添加し、さらに別の生地(セルロース繊維)(綿100%編生地(40番手の綿糸フライス生成り生地))を入れ、浴比(生地:反応溶液=1:30(重量比))にて、実施例6の工程(1a)と同様の反応条件にて、酸化処理を行った。
それ以降の工程は、実施例6と同様の方法によってサンプルを得た。
表6に、上記の製造工程によって製造された各サンプル生地(実施例6~10)についてのカルボキシル基量(COOH基量)、重合度、白度低下、及び反応効率を示す。
なお、カルボキシル基量、重合度、及び反応効率は、前記と同様の方法により測定した。
また、白度は、CIELAB表色系より、L*-3b*として算出(Kollmorgen Instruments Corporation製のMacbeth WHITE-EYE3000微小面積にて測色)した乾燥前と乾燥後の各サンプルの白度の差を測定し、白色低下度とした。なお、絶乾後白度は、「JIS L-0105 4.3」に基づいて絶乾重量を測定した後の白度である。
さらに、表6に示す「生成り」は、精練後の40番手の綿糸フライス生成り生地を示し、「漂白後綿布」は、40番手の綿糸フライス生成り生地を精練後、NaClO2処理とH2O2処理にて漂白し、脱水、乾燥させた綿布である。
表6より、工程(1a)で助触媒として硫酸ナトリウム(ボウ硝)を用いて、TEMPO、及びSDICによるセルロース繊維の酸化処理を行った場合についても、NaClOを用いた実施例1~5と同様、反応溶液の再利用の回数が増えるに従い、反応効率が増大した。
そのため、工程(1a)で使用した反応溶液を再利用する場合、酸化剤としてSDICを用いることも有効であることがわかった。
・工程(1a)
表7に示す反応溶液及び反応条件で、以下の手順で生地(セルロース繊維)の2,2,6,6-テトラメチルピペリジン-N-オキシル(以下、TEMPOとも表記する)、及び次亜塩素酸ナトリウム(NaClO)による酸化処理を行った。なお、生地としては、レーヨン生地(レーヨン40番手の糸を11寸870Nのフライス編機により編成を行い、ベース組織としての1×1ゴム編組織)を用いた。
前記、TEMPO及びNaClOによる酸化処理後、サンプルを反応溶液から取り出し、水洗した。
前記工程(1a)の酸化処理後、水洗したサンプル生地を、さらに表7に示す反応溶液及び反応条件で、亜塩素酸ナトリウム(NaClO2)による酸化処理を行った。なお、表7中のCG1000は、亜塩素漂白用キレート剤(ネオクリスタル(日華化学社製))であり、NaClO2は、25重量%の水溶液を用いた。
表7に示す反応溶液及び反応条件によって工程(2)の酸化処理を行った後、サンプルを取り出し、60℃の水で湯洗いし、さらに水洗した。
前記、工程(2)の酸化処理後、湯洗い、及び水洗を行ったサンプル生地を、さらに表7に示す条件の反応溶液で過酸化水素(H2O2)による脱塩素処理を行った。なお、表7中のPLC7000は、ポリカルボン酸系キレート剤(ネオレート(日華化学社製))であり、H2O2は、35重量%の水溶液を用いた。
前記脱塩素処理を行った後、サンプルを取り出し、60℃の水で湯洗いし、さらに水洗した。それ以降は、実施例1と同様の方法によってサンプルを得た。
実施例11の工程(1a)において、「NaClO(5重量%水溶液) [678%owf(67.8g/L)]」を「NaClO(5重量%水溶液) [783%owf(78.3g/L)]」とした以外は実施例11と同様にしてサンプルを得た。
表8に示す使用溶液及び反応条件で、綿100%編生地(40番手の綿糸フライス生成り綿生地)の マーセライズ加工を行った。
得られたマーセライズ加工済綿生地を用いて、表8に示す反応溶液及び反応条件で、実施例1の手順と同様の方法で工程(1a)、(2)、(3)を行った。それ以降の工程は、実施例1と同様の方法によってサンプルを得た。
工程(1a)において反応時間を4時間とした以外は、実施例13と同様の方法によってサンプルを得た。
二酸化窒素を用いて酸化された酸化再生セルロース(ORC)の編み状の布地(サージセル、登録商標、ジョンアンドジョンソン社)をサンプルとして使用した。
表9に、上記の製造工程によって製造された各サンプル生地(実施例11~14、比較例6)についてのカルボキシル基量(COOH基量)及び重合度を示す。
なお、カルボキシル基量、重合度は、前記と同様の方法により測定した。
表9に示す「レーヨン生成り」は、精練後のレーヨン40番手の糸を11寸870Nのフライス編機により編成を行い、ベース組織としての1×1ゴム編組織の生成り生地を示す。「綿生成り」は、精練後の40番手の綿糸フライス生成り綿生地を示す。
(1)血液吸い上げ試験
サンプルを長さ4cm×幅1cmの短冊状にカットした後、サンプルの下端0.1cmを実験動物血液に1分間浸して観察した。その結果、実験動物血液をサンプル下端0.5cm以上まで吸い上げできた場合を「○」、0.5cm以上の吸い上げが確認できない場合を「×」として評価した。
血液吸い上げ試験における観察で、吸い上げた血液の凝固状況を確認した。血液凝固が確認できた場合を「○」、血液凝固が確認できない場合を「×」として評価した。
サンプルを1×1cmにカットした後、じわじわしみ出すような出血部位に対してサンプルを貼り付けてガーゼで圧迫した。2分間放置し、剥がした後の状態について、操作後出血部位からの出血が全くなかった場合を「○」、出血が続いている場合を「×」として評価した。
出血部位の形状に対する評価として、サンプルの風合いと密着性を評価した。
風合いは、風合い計測システムとして一般的に使われているKES(Kawabata Evaluation System)測定機(カトーテック社製)を用いて、「しなやかさ」を計測した。
密着性は、実際の外科で使用されている方法で評価した。具体的には、サンプル(1×1cm)を剪刃で切り取り出血部位に貼り付けることで密着性を評価した。サンプルを出血部位に貼り付け後、せん断応力を加えても剥離しない場合を「○」、せん断応力で剥離してしまう場合を「×」として評価した。
Claims (18)
- (1a)N-オキシル化合物、酸化剤、及び硫酸ナトリウムを含む反応溶液中で、セルロース繊維を酸化させ、酸化セルロース繊維を得る工程、
(1b)得られた酸化セルロース繊維を分離し、前記反応溶液中にセルロース繊維、及び酸化剤をさらに添加し、再度セルロース繊維を酸化させ、酸化セルロース繊維を得る工程
を含む親水性化セルロース繊維の製造方法。 - 工程(1a)で用いられるN-オキシル化合物が2,2,6,6-テトラメチルピペリジン-N-オキシルである請求項1に記載の親水性化セルロース繊維の製造方法。
- 工程(1a)で用いられるセルロース繊維がレーヨンである請求項1又は2に記載の親水性化セルロース繊維の製造方法。
- 工程(1b)を2回以上行う、請求項1~3のいずれかに記載の親水性化セルロース繊維の製造方法。
- 工程(1a)及び/又は工程(1b)で用いられる酸化剤がハロゲン酸系酸化剤である請求項1~4のいずれかに記載の親水性化セルロース繊維の製造方法。
- 工程(1a)及び/又は工程(1b)で用いられるハロゲン酸系酸化剤が、次亜ハロゲン酸、ハロゲン化イソシアヌル酸又はこれらの塩である請求項5に記載の親水性化セルロース繊維の製造方法。
- (2)工程(1a)及び工程(1b)で得られた酸化セルロース繊維を、酸化剤を含む反応溶液中で酸化させる工程
をさらに含む請求項1~6のいずれかに記載の親水性化セルロース繊維の製造方法。 - 工程(2)で用いられる酸化剤が、ハロゲン酸系酸化剤である請求項7に記載の親水性化セルロース繊維の製造方法。
- 工程(2)で用いられるハロゲン酸系酸化剤が、亜ハロゲン酸又はその塩である請求項8に記載の親水性化セルロース繊維の製造方法。
- (3)工程(2)で得られた酸化セルロース繊維を、脱ハロゲン化剤で脱ハロゲン処理する工程
をさらに含む請求項7~9のいずれかに記載の親水性化セルロース繊維の製造方法。 - (4a)工程(2)によって得られた酸化セルロース繊維を、還元剤を含む反応溶液中で還元させる還元処理工程
をさらに含む請求項7~9のいずれかに記載の親水性化セルロース繊維の製造方法。 - (4b)工程(3)によって得られた酸化セルロース繊維を、還元剤を含む反応溶液中で還元させる還元処理工程
をさらに含む請求項10に記載の親水性化セルロース繊維の製造方法。 - 工程(2)で得られた酸化セルロース繊維を、脱ハロゲン化剤、及び還元剤と混合し、酸化セルロース繊維中に残存するハロゲンを除去する脱ハロゲン処理を行うと共に、酸化セルロース繊維のグルコース単位の2位及び/又は3位に存在するケトン基を還元する還元処理を行う工程
をさらに含む請求項7~9のいずれかに記載の親水性化セルロース繊維の製造方法。 - 脱ハロゲン化剤が、過酸化水素、及びオゾンよりなる群から選ばれる少なくとも1種である請求項10又は13に記載の親水性化セルロース繊維の製造方法。
- 還元剤が、チオ尿素、ハイドロサルファイト、亜硫酸水素ナトリウム、水素化ホウ素ナトリウム、シアノ水素化ホウ素ナトリウム、及び水素化ホウ素リチウムよりなる群から選ばれる少なくとも1種である請求項11~14のいずれかに記載の親水性化セルロース繊維の製造方法。
- N-オキシル化合物、酸化剤、及び硫酸ナトリウムを含む反応溶液中で、セルロース繊維を酸化させ、酸化セルロース繊維を得る工程、及び前記酸化処理工程で使用した反応溶液から酸化セルロース繊維を分離し、前記反応溶液中にセルロース繊維及び酸化剤をさらに添加し、再度セルロース繊維を酸化させることを特徴とする、反応溶液を再利用する方法。
- 請求項1~15のいずれかに記載の親水性化セルロース繊維の製造方法を用いて得られることを特徴とする親水性化セルロース繊維。
- 請求項17に記載の親水性化セルロース繊維を用いて得られる止血材料。
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