CN1280471A - 纤维素基海绵布及其制备方法 - Google Patents
纤维素基海绵布及其制备方法 Download PDFInfo
- Publication number
- CN1280471A CN1280471A CN98811769A CN98811769A CN1280471A CN 1280471 A CN1280471 A CN 1280471A CN 98811769 A CN98811769 A CN 98811769A CN 98811769 A CN98811769 A CN 98811769A CN 1280471 A CN1280471 A CN 1280471A
- Authority
- CN
- China
- Prior art keywords
- weight
- sponge
- cellulose
- sponge cloth
- amine oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 239000001913 cellulose Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims abstract description 35
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229920000297 Rayon Polymers 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims abstract description 13
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- 239000004744 fabric Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 11
- 229920000742 Cotton Polymers 0.000 claims description 7
- 239000012779 reinforcing material Substances 0.000 claims description 7
- -1 inorganic acid salt Chemical class 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 230000003115 biocidal effect Effects 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims 1
- 235000019341 magnesium sulphate Nutrition 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 3
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- 230000015556 catabolic process Effects 0.000 abstract description 2
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- 239000000243 solution Substances 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
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- 238000002360 preparation method Methods 0.000 description 7
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
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- 244000241257 Cucumis melo Species 0.000 description 4
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- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 3
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- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 3
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 2
- 150000001204 N-oxides Chemical class 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 241000282372 Panthera onca Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000843 anti-fungal effect Effects 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 239000013527 degreasing agent Substances 0.000 description 2
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- 239000011777 magnesium Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- WSWCOQWTEOXDQX-MQQKCMAXSA-M (E,E)-sorbate Chemical compound C\C=C\C=C\C([O-])=O WSWCOQWTEOXDQX-MQQKCMAXSA-M 0.000 description 1
- FFYRIXSGFSWFAQ-UHFFFAOYSA-N 1-dodecylpyridin-1-ium Chemical compound CCCCCCCCCCCC[N+]1=CC=CC=C1 FFYRIXSGFSWFAQ-UHFFFAOYSA-N 0.000 description 1
- WLXGQMVCYPUOLM-UHFFFAOYSA-N 1-hydroxyethanesulfonic acid Chemical compound CC(O)S(O)(=O)=O WLXGQMVCYPUOLM-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 125000006177 alkyl benzyl group Chemical group 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N beta-hydroxyethanesulfonic acid Natural products OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
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- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
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- 230000008020 evaporation Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- UPBDXRPQPOWRKR-UHFFFAOYSA-N furan-2,5-dione;methoxyethene Chemical compound COC=C.O=C1OC(=O)C=C1 UPBDXRPQPOWRKR-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- XDAHMMVFVQFOIY-UHFFFAOYSA-N methanedithione;sulfane Chemical compound S.S=C=S XDAHMMVFVQFOIY-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical group COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229940075554 sorbate Drugs 0.000 description 1
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- 229960003080 taurine Drugs 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
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- 239000002023 wood Substances 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/425—Cellulose series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
- B29C67/202—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising elimination of a solid or a liquid ingredient
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2033—Coating or impregnation formed in situ [e.g., by interfacial condensation, coagulation, precipitation, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2525—Coating or impregnation functions biologically [e.g., insect repellent, antiseptic, insecticide, bactericide, etc.]
-
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Abstract
本发明涉及基于纤维素的,进行内部增强且能够按照氧化胺方法获得的海绵布。在此方法中,首先在水氧化胺溶液中制造纤维素的溶液,然后将其与至少一种成孔剂以及纤维混合。将该混合物在传送带上展开,然后引导其通过含稀水氧化胺溶液的凝固浴,该浴的温度足够高,以致该成孔剂熔融并从该溶液溶出。从该溶液洗净剩余的氧化胺,干燥并制造出海绵布网。与粘胶法相对,本发明方法中,聚合物不发生降解,从而改进了海绵布的机械稳定性。也可用塑料网代替该增强纤维。此方法尤其符合生态要求且经济。此海绵布可家用或工业用,特别是用于清洁目的。
Description
本发明涉及已经含有内部增强材料的纤维素基海绵布,并涉及其制造方法。此海绵布高吸水,且用于家庭和工业中的各种清洁和去污目的。
用粘胶法生产海绵布已为人熟知,首先,用氢氧化钠和二硫化碳将浆粕,尤其是木材浆粕,转变为也称粘胶的碱纤维素黄原酸酯溶液。同时用稀释的、含脱脂剂的NaOH使精梳落棉脱脂。然后将熟成的粘胶溶液与棉纤维混合。这一般在捏合机的帮助下完成。除棉纤维外,也有可能用粘胶纤维作为内部增强材料。然后加入格劳伯氏盐(=芒硝)并同样均匀地混合。然后将此海绵布原料涂覆到支撑物上,例如有孔的(foraminous)环形带上,达到需要的任何厚度。也可能将粘胶溶液和格劳伯氏盐的混合物涂覆于塑料支撑材料上,例如聚对苯二甲酸乙二酯(PET)的网上。然后此纤维素在加热的碱凝固浴中进行再生。这也可在酸性介质中完成,例如稀释的硫酸。此方法中,该内部增强材料和该海绵布体变为一体。
格劳伯氏盐熔点很低。因此其在凝固浴中被熔化并被溶解出去。盐晶体的消失遗留下孔和空隙。最后,洗净海绵布以使其无剩余的盐和粘附的反应产物。干燥之后,将其切成窄幅面,接着其被卷起。接着可将此卷材料裁剪成为所需尺寸的布。
然而,粘胶法技术上非常复杂且成本非常高。另外,为了不对环境产生有害影响需要作出极大的努力。伴随粘胶法的不愉快问题是例如形成硫化氢的恶臭味。用粘胶法生产的海绵布仍含有CS2或H2S残余物,其不得不用很高的代价洗净。另外,在粘胶溶液熟成的数小时过程中,纤维素的聚合物链或多或少被降解。这导致纤维素链聚合度(DP)的分布曲线加宽。甚至使用聚合度相同的纤维素起始材料也因此不能一直保证相同的后再生结果。而且海绵布的机械稳定性将尤其随聚合度波动。
本发明的目的是用更加经济和生态性更好的方法制造海绵布,其不合杂质或者至少令人讨厌的杂质明显更少,并且质量一直很高。
可用氧化胺法获得的海绵布达到了此目的。此方法使用纤维素溶于叔胺N-氧化物与水混合物所形成的溶液。尤其适合的N-氧化物是N-甲基吗啉N-氧化物(NMMO)。
氧化胺法是公知的。迄今此方法尤其用于制造纤维素基纤维或薄膜。AT-B 402932(申请号95-02100)描述了纤维素溶解在与成孔剂和发泡剂混合的叔胺氧化物中形成溶液,从该溶液制备纤维素海绵。此混合物露置于发泡剂分解形成气态产物的条件下,并由此产生泡沫而形成较大的空隙。然后此泡沫混合物与水接触以便使纤维素沉淀。可用水从制得的海绵中洗净氧化胺。但是,发泡剂完全不适合海绵布的这种制造,因为它们既不提供所要求的机械稳定性,也不提供必要的抗磨损性。
本发明的海绵布可以通过含有溶解在叔胺N-氧化物和水混合物中的纤维素、成孔剂和纤维增强剂的原料制备而得。该N-氧化物优选是N-甲基吗啉N-氧化物。然后将如此制备的原料经一个喷嘴,优选为狭缝状的喷嘴,涂敷到支撑带上。然后该(优选有孔的)支撑带将它传送到纺丝浴中。该浴含有5-50重量%的水氧化胺溶液,优选含有5-50重量%的水NMMO溶液。该纺丝浴会导致纤维素的沉淀和固化。然后如此制造的海绵布网用水洗净并且干燥。
在另外的实施方案中,将包括成孔剂以及溶于NMMO和水的纤维素的材料从两侧施加到网状材料,例如聚酯网上。然后如此涂敷的网通过所述的纺丝和洗涤浴。然而,两者中任一种情形都要求内部增强。相反,在纤维素海绵中,内部增强仅起着有利于提高水吸附能力的次要作用。
由本发明方法制备的海绵布-在其它一般条件都相同时-和由粘胶法制备的海绵布相比,机械稳定性更高且从而断裂强度更高。其原因主要是本发明方法中,没有发生粘胶溶液熟成时不可避免的聚合物降解。本发明纤维素产品中纤维素的分子量分布曲线与本方法中所用纤维素原料的分子量分布曲线实际上是一致的。而且,因为溶液制备与其凝固之间的时间被延长条件下也不会发生聚合物降解,故可以确保质量一致。本发明的海绵布实际上没有不受欢迎的杂质如硫化氢和二硫化碳。其可以吸附并保持大量的水。而且它通常可自然降解,因此能没有问题地堆肥处理。
海绵布制备中所用的氧化胺实际上可定量回收并-经适当浓缩后-可被回用。因此在海绵布原料中的氧化胺与在纺丝浴以及在随后浴液中的氧化胺相同是具有优越性的。剩余的污水中几乎不含任何残渣,并且因此其仅有低的化学需氧量(COD)。
本发明方法中的成孔剂优选为易溶于水的无机盐。特别有用的是碱金属、碱土金属和铵的无机酸盐,如氯化物(尤其是NaCl和KCl但不是MgCl2)、硫酸盐(尤其是Na2SO4和MgSO4)、磷酸盐(尤其是Mg3(PO3)2)、硅酸盐(尤其是Mg2[SiO4]=镁橄榄石)以及碳酸盐(尤其是Na2CO3、CaCO3和(NH4)2CO3)。这些盐晶体的直径通常至多2.5mm,优选至多2.0mm。但仅有大约1/5的该晶体直径小于0.3mm,否则所得海绵布的水吸附能力会降低。成孔剂的百分率通常占海绵布原料总重量的30-90重量%,优选占70-85重量%。
合适的纤维素源为桨粕,特别是碎木桨。本发明方法所用纤维素的聚合度DP为300~1600,优选为400~600。该纤维素与含水NMMO(水的百分率约为40重量%)混合的最初结果是形成悬浮液。然后在减压(优选大约40~200mbar)下搅拌并加热(大约70~120℃,优选85~95℃)该悬浮液以除去一些水。水所占的百分率由大约为40重量%降到大约7~12重量%,并且该悬浮液实际上转化为均质的溶液。该溶液的折射率为约1.4910~1.4930。该溶液中含5~20重量%,优选10~15重量%的溶解纤维素,此溶液的粘度为大约1500Pas。当新制备时,该溶液仅为弱碱性(pH约7.8)。然而静置后,NMMO分解成碱性产物,其使pH值升高。特别是在WO 97/31970中描述了纤维素溶液的制备。然后该纤维素溶液与其它组分混合,在捏合机中进行有利。这样制造的海绵布原料中,纤维素的百分率为该原料总重量的0.5~10.0重量%,优选为1.0~5.0重量%。
纤维增强材料包括天然纤维,优选棉、大麻、亚麻或者用NMMO方法制造的粘胶纤维(lyocell)。纤维长度为5~50mm,优选为10~30mm。这些纤维通常要经过预处理以改善与NMMO的相容性。该纤维的百分率为海绵布干重的5~50重量%,优选10~40重量%。
海绵布在干态时比较脆。要克服这个缺点,可以向海绵布原料中添加增塑物质。特别有效的增塑剂仅可被非常缓慢地洗出,果真如此,则在整个使用期间,可以保持其理想的效果。有用的增塑剂特别是淀粉以及淀粉的衍生物、低分子量纤维素衍生物、聚乙烯醇、乙烯基吡咯烷酮/乙烯醇的共聚物、聚醋酸乙烯酯、乙烯基甲醚/马来酸酐的共聚物(Gantrez)、脲、己二胺-[1,6]、角叉菜胶、藻酸盐(特别是藻酸钠),瓜尔(guar)及瓜尔的衍生物[特别是瓜尔的阳离子衍生物(Meyprofloc),羧甲基羟丙基瓜尔(Jaguar CMHP)以及高取代的羧甲基瓜尔(Jaguar CMHS)]、半乳甘露聚糖、黄原胶、带有侧链的多糖(Rhodigel)、杂多糖(Rhodicare)、烷基聚乙氧基铵的乳酸盐(alkylpolyethoxyammonium lactate)(Genamin)、聚酯的互聚物(Cassapret)、磷酸酯(Hostaphat)、基于不同链长的饱和或不饱和脂肪酸与牛磺酸、甲基牛磺酸或羟基乙烷磺酸、N-椰子基谷氨酸(N-cocoylg1utamic acid)单钠盐的缩聚产物(Hostapon),脂肪醇聚乙二醇醚(Genapo1),邻苯二甲酸的二酯或四氮化合物(Leomin)。该增塑剂占制成的海绵布干重的百分率为1~15重量%,优选为2~10重量%。
还可将本发明的海绵布最后浸渍到杀生物-特别是杀真菌、杀细菌和/或杀藻-活性的物质中(参见DE-U 296 18 058)。当变潮湿的海绵布可能要在薄膜包装中保留延续的一段时间时,进行杀生物整理是特别明智的。特别优选的杀生物剂是异噻唑啉酮(isothiazo1one)、苯并异噻唑啉酮(benzisothiazolone)和苯并咪唑的衍生物。杀真菌或杀细菌活性也可以由阳离子的、表面活性铵盐呈现出来,其具有长链、饱和或不饱和的(C6~C24)烷基,特别是氯化(C8~C18)烷基三甲铵、氯化双(C10~C18)烷基二甲铵或氯化烷基苄基二甲铵。除叔铵化合物的氯化物外,然而,也可使用溴化物,醋酸盐,丙酸盐,山梨酸盐,苯甲酸盐或硫酸盐。这些化合物的描述见于例如EP-A 286009中。杀细菌活性最终也可由双吡啶基硫化物和它的双-N-氧化物或者1-烷基-和1-烯基吡啶翁盐(例如氯化1-月桂基吡啶翁)呈现。类似地,其中混入了银或铜的硅铝酸盐或沸石(得自日本Shinanen Zeomic Co.Ltd.,的Zeomic,CAS No.1318-02-1)也显示杀生物的效果。也可经甘油或丙二醇浸渍达到同样的效果。
最后,本发明的海绵布还可被润湿。特别有用的加湿剂是2~8重量%的氯化镁溶液,该溶液可以另外包括0.2重量%乳化形式的香料,例如有柠檬、松木或类似香味的油。
本发明还提供基于纤维素并且具有内部增强的海绵布的制备方法,其包括如下步骤:
(a)提供包括溶于叔胺N-氧化物和水的纤维素并还至少包括一种成孔剂以及纤维的混合物,
(b)将该混合物在传送带上展开,
(c)用含稀水氧化胺溶液的凝固浴处理该层,以便溶出成孔剂。
(d)将剩余的氧化胺洗去,
(e)干燥该海绵布网并
(f)将其裁剪。
在捏合机中混合这些独立成分可更为有利地制备该海绵布原料。最后混入成孔剂和任何有色颜料是有利的。用例如狭缝喷嘴可有效地在传送带上展开此原料。
本领域的熟练人员会明白,进行裁剪主要是将潮湿或干燥海绵布的长度切断成所需要尺寸以及进行或不进行印花地包装等操作。
本发明的一个变体中,变更了步骤(a)和(b)。步骤(a)省去纤维;另外,步骤(b)包括经喷嘴以薄层向塑料网的两侧施加混合物。
用以下的实施例举例说明本发明。除非另外说明,否则百分率为重量百分率。
实施例1
将510克平均聚合度为535(用铜氨液法测定)的研磨木桨粕(Cellunier F得自Rayonier)浸泡在5087克60%的NMMO溶液中。然后,用NaOH将该浸泡液的pH值调整到11。然后将该浸泡液在减压下搅拌并加热升高温度,以便蒸馏除去水,直到NMMO的浓度为水和NMMO总重量的87.7%,并出现一水合物(从折射率为1.4820可分辨出)为止。在此持续大约4个小时的时期里,真空度保持在10~16托。经过大约85~95℃另外2~3小时的搅拌后,全部桨粕已变为溶液。
为使少量的水蒸发,在此阶段将该真空度调整到大约200托。此时,折射率固定在大约1.4910~1.4930,这相应于含水7.5~9%。
将如此制备的溶液与850克被苛性钠和脱脂剂构成并适当加热的溶液湿润的棉混合并且捏合。在第二次捏合加工中,该桨粕-棉溶液与30千克氯化钠成孔剂和3克蓝色颜料混合,同时维持能确保必要流动性的温度。
所得海绵布性能如下:
实施例2
性能 | 单位 | 数值 | 标准 |
基本重量 | g/m2 | 263 | DIN53 854(绝干) |
湿态厚度 | 5.3 | DIN53 855,0.02N/cm2 | |
干态厚度 | mm | 2.4 | DIN53 855,0.2N/cm2 |
水吸附容量 | l/m2 | 5.4 | |
Veslic实验 | 磨擦周期 | 98 | |
磨耗值 | g/m2 | 41 | DIN53 528 |
湿极限拉伸应力强度 | N/15mm | 25 | DIN EN ISO 527-1 |
湿极限拉伸应力伸长率 | % | 19 | DIN EN ISO 527-1 |
重复实施例1,不同的是成孔剂(NaCl)的量减为25千克。所得海绵布性能如下:
性能 | 单位 | 数值 | 标准 |
基本重量 | g/m2 | 380 | DIN53 854(绝干) |
湿态厚度 | mm | 5.9 | DIN53 855,0.02N/cm2 |
干态厚度 | mm | 2.8 | DIN53 855,0.2N/cm2 |
水吸附容量 | l/m2 | 6.3 | |
Veslic实验 | 磨擦周期 | 112 | |
磨耗值 | g/m2 | 38 | DIN53 528 |
湿极限拉伸应力强度 | N/15mm | 30 | DIN EN ISO 527-1 |
湿极限拉伸应力伸长率 | % | 25 | DIN EN ISO 527-1 |
Claims (16)
1.一种基于纤维素并且已含有内部增强材料的海绵布,可通过氧化胺方法获得。
2.权利要求1的海绵布,其中该方法中所使用的氧化胺为N-甲基吗啉N-氧化物。
3.权利要求1或2的海绵布,其中所述内部增强材料包括棉纤维、粘胶纤维或者聚合物网。
4.权利要求1至3中一项或多项的海绵布,包括至少一种增塑剂。
5.权利要求1至3中一项或多项的海绵布,将其用杀生物活性剂浸渍。
6.基于纤维素并已含有内部增强材料的海绵布的制造方法,该方法包括(a)提供包括溶解在叔胺N-氧化物和水中的纤维素并且还包括至少一种成孔剂以及纤维的混合物,(b)将该混合物在传送带上展开,(c)使该层通过含稀水氧化胺溶液的凝固浴,溶出该成孔剂,(d)洗净剩余的氧化胺,(e)干燥该海绵布网并且(f)将它裁剪。
7.基于纤维素并有内部增强材料的海绵布的制造方法,该方法包括(a)提供包括溶解在叔胺N-氧化物和水中的纤维素并且还包括至少一种成孔剂的混合物,(b)将该混合物涂覆到聚合物网的双面上,(c)使该层通过含稀水氧化胺溶液的凝固浴,溶出该成孔剂,(d)洗净剩余的氧化胺,(e)干燥该海绵布层并且(f)将其裁剪。
8.权利要求6或7的方法,其中该叔胺N-氧化物为N-甲基吗啉N-氧化物。
9.权利要求6或7的方法,其中该凝固浴含5~50重量%的水氧化胺溶液,优选5~50重量%的水NMMO溶液。
10.权利要求6的方法,其中该纤维的百分率为该海绵布干重的5~50重量%,优选10~40重量%。
11.权利要求6或7的方法,其中该成孔剂为碱金属的、碱土金属的或者铵的无机酸盐。
12.权利要求11的方法,其中该成孔剂为硫酸钠或者硫酸镁。
13.权利要求6或7的方法,其中该成孔剂的百分率为该海绵布原料总重量的30~90重量%,优选70~85重量%。
14.权利要求6或7的方法,其中该纤维素的百分率为该海绵布原料总重量的0.5~10.0重量%,优选1.0~5.0重量%。
15.权利要求6或7的方法,其中该混合物另外包括至少一种增塑剂和/或至少一种杀生物活性剂。
16.权利要求6或7的方法,其中该增塑剂的百分率为制成的海绵布干重的1~15重量%,优选2~10重量%。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19753546.1 | 1997-12-03 | ||
DE19753546A DE19753546A1 (de) | 1997-12-03 | 1997-12-03 | Schwammtuch auf Cellulosebasis und Verfahren zu dessen Herstellung |
Publications (2)
Publication Number | Publication Date |
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CN1280471A true CN1280471A (zh) | 2001-01-17 |
CN1147271C CN1147271C (zh) | 2004-04-28 |
Family
ID=7850562
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CNB98811769XA Expired - Fee Related CN1147271C (zh) | 1997-12-03 | 1998-11-25 | 纤维素基海绵布及其制备方法 |
Country Status (11)
Country | Link |
---|---|
US (1) | US7189667B1 (zh) |
EP (1) | EP1035794B1 (zh) |
JP (1) | JP4318853B2 (zh) |
CN (1) | CN1147271C (zh) |
AT (1) | ATE213602T1 (zh) |
BR (1) | BR9815153A (zh) |
DE (2) | DE19753546A1 (zh) |
ES (1) | ES2173658T3 (zh) |
HK (1) | HK1034177A1 (zh) |
NO (1) | NO20002771D0 (zh) |
WO (1) | WO1999027835A1 (zh) |
Cited By (5)
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CN105237796A (zh) * | 2015-10-30 | 2016-01-13 | 江苏赛维环保有限公司 | 一种纤维多孔材料制备方法 |
CN107033392A (zh) * | 2017-03-28 | 2017-08-11 | 常州大学 | 一种高纳污清洁海绵的制备方法 |
CN107326530A (zh) * | 2017-06-15 | 2017-11-07 | 东华大学 | 一种增材制造棉纤维面料的制备方法 |
CN108219502A (zh) * | 2018-01-31 | 2018-06-29 | 陈长飞 | 一种浆料组合物、环保抹布制备方法及环保抹布 |
CN110577666A (zh) * | 2018-06-07 | 2019-12-17 | 淮安市冰青建设工程管理有限公司 | 一种环保型纤维素海绵材料 |
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AT410319B (de) * | 2001-07-25 | 2003-03-25 | Chemiefaser Lenzing Ag | Celluloseschwamm und verfahren zu dessen herstellung |
DE10247241A1 (de) * | 2002-10-10 | 2004-04-22 | Basf Ag | Superabsorbierender Schaum, Verfahren zu seiner Herstellung und seine Verwendung |
DE102004011287A1 (de) | 2004-03-09 | 2005-09-22 | Kalle Gmbh | Schallschutzelement aus mindestens zwei Schichten, Verfahren zu seiner flammhemmenden Ausrüstung und seine Verwendung |
EP1729623B1 (de) * | 2004-03-23 | 2012-11-28 | Kalle GmbH | Schwammtuch auf zellulosebasis und verfahren zur herstellung eines schwammtuches |
DE102004029486A1 (de) * | 2004-06-18 | 2006-01-05 | Stefan Berger | Verwendung einer Schwammtuchmatte aus einem Cellulose-Baumwollfasergemisch als aushärtbarer Formkörper |
DE102005007270A1 (de) | 2005-02-17 | 2006-08-24 | Kalle Gmbh | Schwammtuch, Verfahren zu seiner Herstellung und seine Verwendung |
WO2009023864A1 (en) * | 2007-08-15 | 2009-02-19 | Rebecca Berrigan | Biodegradable shower mat |
DE102008007475A1 (de) * | 2008-02-04 | 2009-08-06 | Kalle Gmbh | Bindemittel zur Aufnahme von Flüssigkeiten, insbesondere Öl |
US10136656B2 (en) | 2010-10-01 | 2018-11-27 | The Hillshire Brands Company | Systems and methods for providing a food product with additives |
KR20120094922A (ko) | 2009-09-30 | 2012-08-27 | 튀링기셰스 인슈티투트 퓌르 텍스틸-운트 쿤스트슈토프-포르슝 이.브이. | 클래딩 재료 및 캐리어 재료를 갖는 성형체 및 이의 제조 방법 |
DE102010012878A1 (de) | 2010-03-26 | 2011-09-29 | Kalle Gmbh | Schwammtuch mit Netz |
CN101792538A (zh) * | 2010-04-02 | 2010-08-04 | 山东海龙股份有限公司 | 一种采用离子液体生产纤维素海绵的方法 |
CN101942112B (zh) * | 2010-09-09 | 2012-07-25 | 宁波尼可家用品有限公司 | 一种竹浆海绵制品及其制备方法 |
US9380804B2 (en) | 2012-07-12 | 2016-07-05 | The Hillshire Brands Company | Systems and methods for food product extrusion |
AT514473B1 (de) | 2013-06-19 | 2016-06-15 | Chemiefaser Lenzing Ag | Neues umweltschonendes Verfahren zur Herstellung von Schwämmen und Schwammtüchern aus Polysacchariden |
AT514472B1 (de) | 2013-06-19 | 2016-03-15 | Lenzing Akiengesellschaft | Neues umweltschonendes Verfahren zur Herstellung von Schwämmen und Schwammtüchern aus Polysacchariden |
DE202015101364U1 (de) | 2015-03-17 | 2015-03-20 | Kalle Gmbh | Cellulose-Schwammtuch mit abrasiven Eigenschaften |
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US2179181A (en) * | 1936-04-21 | 1939-11-07 | Soc Of Chemical Ind | Cellulose solutions and process of making same |
DE2711698C3 (de) * | 1977-03-17 | 1980-03-27 | Hoechst Ag, 6000 Frankfurt | Zum Scheuern und zur Naßreinigung geeignete Vorrichtung |
US4145532A (en) * | 1977-11-25 | 1979-03-20 | Akzona Incorporated | Process for making precipitated cellulose |
FR2629334B1 (fr) * | 1988-03-30 | 1991-09-13 | Spontex Sa | Materiau cellulosique alveolaire essuyant |
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AT400581B (de) * | 1993-10-19 | 1996-01-25 | Chemiefaser Lenzing Ag | Verfahren zur herstellung von lösungen von cellulose |
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AT402932B (de) * | 1995-12-22 | 1997-09-25 | Chemiefaser Lenzing Ag | Celluloseschwamm und verfahren zu dessen herstellung |
FR2748277B1 (fr) * | 1996-05-06 | 1998-07-31 | Elysees Balzac Financiere | Procede de fabrication de produits alveolaires cellulosiques produits alveolaires cellulosiques |
DE19623703C1 (de) * | 1996-06-14 | 1997-07-24 | Freudenberg Carl Fa | Schwamm und Verfahren zu dessen Herstellung |
DE29618058U1 (de) * | 1996-10-18 | 1997-01-23 | Kalle Nalo GmbH, 65203 Wiesbaden | Biocid ausgerüstetes Schwammtuch |
GB9626894D0 (en) * | 1996-12-24 | 1997-02-12 | Courtaulds Fibres Holdings Ltd | Cellulosic sponges |
-
1997
- 1997-12-03 DE DE19753546A patent/DE19753546A1/de not_active Withdrawn
-
1998
- 1998-11-25 AT AT98963512T patent/ATE213602T1/de not_active IP Right Cessation
- 1998-11-25 JP JP2000522827A patent/JP4318853B2/ja not_active Expired - Fee Related
- 1998-11-25 BR BR9815153-3A patent/BR9815153A/pt not_active IP Right Cessation
- 1998-11-25 US US09/554,733 patent/US7189667B1/en not_active Expired - Fee Related
- 1998-11-25 ES ES98963512T patent/ES2173658T3/es not_active Expired - Lifetime
- 1998-11-25 CN CNB98811769XA patent/CN1147271C/zh not_active Expired - Fee Related
- 1998-11-25 EP EP98963512A patent/EP1035794B1/de not_active Revoked
- 1998-11-25 WO PCT/EP1998/007599 patent/WO1999027835A1/de active IP Right Grant
- 1998-11-25 DE DE59803234T patent/DE59803234D1/de not_active Revoked
-
2000
- 2000-05-30 NO NO20002771A patent/NO20002771D0/no unknown
-
2001
- 2001-07-10 HK HK01104750A patent/HK1034177A1/xx not_active IP Right Cessation
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105237796A (zh) * | 2015-10-30 | 2016-01-13 | 江苏赛维环保有限公司 | 一种纤维多孔材料制备方法 |
CN107033392A (zh) * | 2017-03-28 | 2017-08-11 | 常州大学 | 一种高纳污清洁海绵的制备方法 |
CN107326530A (zh) * | 2017-06-15 | 2017-11-07 | 东华大学 | 一种增材制造棉纤维面料的制备方法 |
CN108219502A (zh) * | 2018-01-31 | 2018-06-29 | 陈长飞 | 一种浆料组合物、环保抹布制备方法及环保抹布 |
CN110577666A (zh) * | 2018-06-07 | 2019-12-17 | 淮安市冰青建设工程管理有限公司 | 一种环保型纤维素海绵材料 |
Also Published As
Publication number | Publication date |
---|---|
JP2001524338A (ja) | 2001-12-04 |
WO1999027835A1 (de) | 1999-06-10 |
BR9815153A (pt) | 2000-10-10 |
NO20002771L (no) | 2000-05-30 |
DE19753546A1 (de) | 1999-06-10 |
NO20002771D0 (no) | 2000-05-30 |
ES2173658T3 (es) | 2002-10-16 |
DE59803234D1 (de) | 2002-04-04 |
CN1147271C (zh) | 2004-04-28 |
US7189667B1 (en) | 2007-03-13 |
HK1034177A1 (en) | 2001-10-19 |
ATE213602T1 (de) | 2002-03-15 |
JP4318853B2 (ja) | 2009-08-26 |
EP1035794B1 (de) | 2002-02-27 |
EP1035794A1 (de) | 2000-09-20 |
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