US3297399A - Process of mercerizing a cellulosic material while simultaneously depositing silica thereon - Google Patents
Process of mercerizing a cellulosic material while simultaneously depositing silica thereon Download PDFInfo
- Publication number
- US3297399A US3297399A US154357A US15435761A US3297399A US 3297399 A US3297399 A US 3297399A US 154357 A US154357 A US 154357A US 15435761 A US15435761 A US 15435761A US 3297399 A US3297399 A US 3297399A
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- US
- United States
- Prior art keywords
- thread
- silica
- caustic
- mercerization
- fibers
- 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.)
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 140
- 239000000377 silicon dioxide Substances 0.000 title claims description 57
- 238000000034 method Methods 0.000 title claims description 38
- 239000000463 material Substances 0.000 title claims description 22
- 238000000151 deposition Methods 0.000 title 1
- 239000003518 caustics Substances 0.000 claims description 40
- 238000005517 mercerization Methods 0.000 claims description 33
- 239000000835 fiber Substances 0.000 claims description 30
- 239000008119 colloidal silica Substances 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 22
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 239000002657 fibrous material Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000080 wetting agent Substances 0.000 description 18
- 235000002639 sodium chloride Nutrition 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229920000742 Cotton Polymers 0.000 description 8
- -1 sodium alkyl sulfates Chemical class 0.000 description 8
- 238000001246 colloidal dispersion Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- JEUFWFJKIXMEEK-UHFFFAOYSA-N carboxy-[2-(dicarboxyamino)ethyl]carbamic acid Chemical class OC(=O)N(C(O)=O)CCN(C(O)=O)C(O)=O JEUFWFJKIXMEEK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- VAAMTBVAVRTUHW-UHFFFAOYSA-N ethane-1,2-disulfonic acid N-methyloctadecanamide Chemical compound S(=O)(=O)(O)CCS(=O)(=O)O.C(CCCCCCCCCCCCCCCCC)(=O)NC VAAMTBVAVRTUHW-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009950 felting Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- RLJSXMVTLMHXJS-UHFFFAOYSA-M sodium;4-decylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 RLJSXMVTLMHXJS-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67383—Inorganic compounds containing silicon
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- D06M11/32—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
- D06M11/36—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 oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- D06M11/51—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
- D06M11/55—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 trioxide; with sulfuric acid or thiosulfuric acid or their salts
- D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- D06M11/68—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
- D06M11/71—Salts of phosphoric acids
-
- D—TEXTILES; PAPER
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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
- D06M11/77—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 silicon or compounds thereof
- D06M11/79—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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—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 oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—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 sulfur or phosphorus
- D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
- D06M13/252—Mercaptans, thiophenols, sulfides or polysulfides, e.g. mercapto acetic acid; Sulfonium compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—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 sulfur or phosphorus
- D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
- D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—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 sulfur or phosphorus
- D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
- D06M13/262—Sulfated compounds thiosulfates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—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 sulfur or phosphorus
- D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
- D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- 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
- D06M13/325—Amines
- D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- 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
- D06M13/46—Compounds containing quaternary nitrogen atoms
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- 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
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
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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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Definitions
- This invention relates to textile yarns and threads and a process for producing the same, and more particularly to yarns and threads that have been produced by treating them with colloidal silica and mercerization in order to impart enhanced desirable characteristics to said yarns and threads. 7
- the yarns and threads of the invention are characterized by increased tensile strength, added lustre, more smoothness or a gassed effect, and reduced static, which allows the individual ends to be separated more easily in the subsequent quilling operation.
- the immersion of the yarn and thread in a silica bath, followed by drying, deposits particles of silica on the individual fibers, which results in an increase of the coefficient of friction of the individual fibers, which in turn results in a reduction of elongation because the frictionally held fibers break under added tension rather than elongating sulficiently to mercerize the yarn and thread.
- Single and or unplied yarns have been especially noted for their fragility, and heretofore no one has been able to successfully mercerize a low twist, unplied or single end, spun yarn.
- low twist is meant single end spun yarns having a twist multiple of about 3.25 and lower.
- the present invention comprises a continuous process whereby yarn or thread is immersed in a colloidal dispersion of silica and then passed immediately in its wet condition into the caustic of a mercerization bath.
- the caustic of the mercerization bath precipitates the silica from the colloidal dispersion onto the fibers while they are being shrunk or mercerized by the caustic.
- yarns and threads by the invention can be dyed evenly and uniformly because the uniformity of tension throughout the yarns and threads, along with mercerization, increases their alfinityfor dye.
- the process allows single end or unplied yarns to be mercerized because they are strengthened by the silica treatment while being mercerized.
- the present invention also permits the use of greater tensioning during mercerization with consequent increased strength of the mercerized thread or yarn, as welljas other desirable properties such as Wrinkle resistance for single yarns and crease retention on plied yarns.
- Describing the method of the present invention in greater detail comprises the steps of immersing the cotton yarn or thread in a bath of, or otherwse treating it so as to impregnate it thoroughly with, an aqueous dispersion of colloidal silica containing approximately l% by weightof-silica.
- the bath is maintained at a temperature of about 200% F. and the pH is about 11.0, although under.certainconditions; e.g., where contamination of the caustic baths is no problem, a pH of as low as about 9.8 can be used.
- the colloidal silica bath also is preferably provided with a small percentage, e.g., 0.5%, of a detergent or'wetting agent in order to enforce the impregnation of the fibers, in which case the temperature of the bath can be maintained at a somewhat lower temperature, e.g,, about F.
- a detergent or'wetting agent e.g. 0.5%
- the wetting agent maybe used of a wide variety of compounds, such asfor example the sodium salts of alkylated benzene sulfonates such as sodium oct-yl benezene sulfonate and sodium-decyl benzene sulfonate; sodium lauryl sulfate, the.
- wetting agent which has been found especially suitable for the present purposes is any one of a group of higher sodium alkyl sulfates possessing powerful Wetting and emulsifying properties. They are stable in the presence of'ac'ids, alkalies, salts, and hard water and they markedly reducethe surface activity of water solutions eve'n under conditions of high dilution. They are used in kier boiling, mercerizing, carbonizing, felting and scouring and dyeing operations, and in the manufacture of bactericides and anticeptics.
- the thread or yarn is subjected to the caustic of a mercerization bath while still in the wet condition, which simultaneously mercerizes the thread and deposits silica in the fibers thereof.
- the thread or yarn can. be first treated With a bath containing about 1% caustic and one of the above wetting agents in the aforementioned proportions; then rinsed with hot water at about F.'to remove the caustic from the surface of the yarn so none will contaminate the colloidal silica bath, and then passed through the colloidal silica bath at a pH of about 9.8, with subsequent vmercerizing treatment as described previously.
- This sequence of steps tends to initiate precipitation or cause partial precipitation of the. silica prior to the mercerization step which may be desired under certain conditions.
- Another variation is to treat first with water at 190 F. then with the colloidal silica, next with a 1% caustic treat, followed by meroerization. In this way, one can obtain partial or complete precipitation of the silica prior to flarezation as desired.
- Still another variation is to first treat with a solution of about 1% wetting agent in water at 150 F then treat with the silica bath at about 190 F., followed by mercerization.
- One object in subjecting the cellulosic and blended materials to the above process steps prior to mercerization is generally to bring the colloidal suspension on the fibers to a more or less unstable condition so that precipitation of the silica will take place rapidly when the material contacts the caustic of 'the mercerization treatment.
- partial precipitation or instability may be brought about by treatment with one or more of the following types of compounds prior to, during, or after the colloidal silica treatment and before the mercerization step: alkali metal salts of strong organic and inorganic and weak acids, eag. sodium chloride, magnesium sulfate, magnesium phosphate, sodium phosphate, etcj; higher fatty'amine salts, quaternary ammonium, sulfoniurn and phosphonium compounds, alkali salts of ethylenediaminetetracarboxylic acids, and the like.
- alkali metal salts of strong organic and inorganic and weak acids eag. sodium chloride, magnesium sulfate, magnesium phosphate, sodium phosphate, etcj
- higher fatty'amine salts quaternary ammonium, sulfoniurn and phosphonium compounds
- alkali salts of ethylenediaminetetracarboxylic acids and the like.
- the warps were then passed through squeeze rolls-and into another vat containing an identical colloidal dispersion of silica at 200 'F., then through squeeze rolls and into a vat containing water at room temperature, then through squeeze rolls and into a vat containing a 23% aqueous solution of NaOH, all parts by weight, at room temperature.
- the yarn was next passed through squeeze rolls and into a vat containing water at 135 F., then through squeeze rolls and into a vat containing water at 110 F., then through squeeze rolls and into a vat containing water at room temperature, then through squeeze rolls and into a vat containing a 1 /2% aqueous solution of H 50 by volume, at room temperature.
- the yarn was passed through squeeze rolls and into a vat containing a 1 /2% aqueous solution of H 80 by volume, at room temperature, then through squeeze rolls and into a vatcontaining water at room temperature, then through squeeze rolls and into a vat containing water at room temperature, then through squeeze rolls and into a vat containing enough aqueous solution of ammonia at room temperature to adjust the pH of the yarn to about pH 7, then through squeeze rolls and into a bath containing water at 80 F, then through squeeze rolls and into a vat containing water at 140 F., then through squeeze rolls and into a loop dryer at 175 F. until substantially dry.
- the resultant yarn had the previously described improved properties.
- the above is a continuous process carried out on a conventional warp mercerizing range.
- a 37s two cord cotton thread was treated according to the method of Example I, with the exception that the thread was given a water wash at 190 F. prior to the silica treatment, the water wash just prior to the caustic treatment was eliminated, and the caustic was refrigerated to maintain it at 70 F.
- the thread showed a remarkable improvement in uniformity of elongation, compared with the untreated thread.
- Five bobbins. selected at random were tested twenty times each for elongation on a Uster single end testing machine. In the following table, each elongation figure represents the average of the twenty figures obtained for each bobbin at break:
- EXAMPLE II Fifty warps of l8s single combed cotton yarn, each warp containing 378 ends properly base, were treated identically as described in Example 1 above, except that the final vat of wash water has a temperature of 100 F., rather than 140 F. Similar enhancement of properties was obtained.
- EXAMPLE III Fifty warps of 37s two ply combed cotton thread, each warp containing 378 ends, were treated identically as described in Example I above. Once again the desired properties were achieved.
- EXAMPLE IV Fifty warps of 18s single combed spun yarn, made from a blend of 75% cotton and 25% viscose rayon, were treated identically as described in Example II above and similar improvement in properties was noted.
- the improvement in breaking strength was thus shown to be about 33%.
- the method of producing an improved cellulose containing fibrous material having increased tensile strength, added lustre, greater smoothness and improved receptivity -to dyes comprising the steps of treating said material with an aqueous dispersion of colloidal silica and thereafter subjecting such silica treatedmaten'al while in the wet condition to the caustic of a mercerization bath simultaneously to mercerize said material and to deposit silica on the fibers thereof.
- the method of producing an improved cellulose containing fibrous material comprising the steps of treating said material with an aqueous dispersion of colloidal silica containing about 1% by weight of silica, thereafter subjecting the treated material while in the Wet condition to the caustic of a mercerization bath simultaneously to Inercerized said material and to deposit silica in the fibers thereof.
- the method of producing an improved cellulosic thread comprising the steps of treating said thread with an aqueous dispersion of colloidal silica containing about 1% by weight of silica at a temperature of about 200 F., thereafter subjecting the treated thread while in the wet condition to the caustic of a mercerization bath simultaneously to mercerize said thread and to deposit silica in the fibers thereof.
- the method of producing an improved cellulosic thread comprising the steps of treating said thread with an aqueous dispersion of colloidal silica containing about 1% by weight of silica at a temperature of about 200 F. and having a pH of about 11.0, thereafter subjecting the treated thread while in the wet condition to the caustic of a mercerization bath simultaneously to mercerize said thread and to deposit silica in the fibers thereof.
- the method of producing an improved cellulosic thread comprising the steps of treating said thread with an aqueous dispersion of colloidal silica containing about 1% by weight of silica at a temperature of about 200 F. and having a pH of about 11.0, then removing the excess aqueous dispersion from said thread thereafter subjecting the treated thread while in the wet condition to the caustic of a mercerization bath simultaneously to mercerize said thread and to deposit silica in the fibers thereof.
- the method of producing an improved cellulosic thread comprising the steps of treating said thread with an aqueous dispersion of colloidal silica containing about 1% by weight of silica at a temperature of about 200 F. and having a pH of about 11.0, then passing said thread through squeeze rolls, thereafter subjecting the treated thread while in the wet condition to the caustic of a mercerization bath simultaneously to mercerize said thread and to deposit silica in the fibers thereof.
- the method of producing an improved cellulosic thread comprising the steps of immersing said thread in a bath containing an aqueous dispersion of colloidal silica and a wetting agent, thereafter subjecting the thread while in the wet condition to the caustic of a mercerization bath simultaneously to mercerize said thread and to deposit silica on the fibers thereof.
- the method of producing an improved cellulosic thread comprising the steps of immersing said thread in a bath containing an aqueous dispersion of colloidal silica having about 1% by weight of silica and about 0.1 to 5.0% by weight of a wetting agent, thereafter subjecting the thread While in the wet condition to the caustic of a mercerization bath simultaneously to mercerize said thread and to deposit silica on the fibers thereof.
- the method of producing an improved cellulosic thread comprising the steps of immersing said thread in a bath containing an aqueous dispersion of colloidal silica having about 1% by Weight of silica and about 0.1 to 5.0% by weight of a wetting agent having the formula C H CH C H C H CH (SO Na C H CH (C 11 2 thereafter subjecting the thread while in the wet condition to the caustic of a mercerization bath simultaneously to mercerize said thread and to deposit silica on the fibers thereof.
- the method of producing an improved cellulosic thread comprising the steps of immersing said thread in a bath containing an aqueous dispersion of colloidal silica having about 1% by weight of silica and about 0.1 to 5.0% by weight of a wetting agent having the formula C H CH(C H )C H CH(SO N21)C H CH(C H aid 6 bath having a temperature of about F. and a pH of about 11.0, thereafter subjecting the thread while in the Wet condition to the caustic of a mercerization bath simultaneously to mercerize said thread and to deposit silica on the fibers thereof.
- a wetting agent having the formula C H CH(C H )C H CH(SO N21)C H CH(C H aid 6 bath having a temperature of about F. and a pH of about 11.0
- the method of producing a cellulosic thread having improved properties comprising the steps of treating said thread with a solution containing 1% by weight of caustic and about 0.1 to 5.0% by weight of an anionic wetting agent, then rinsing said thread with water to remove the caustic from the surface of the thread, next treating said thread with an aqueous dispersion of colloidal silica, thereafter subjecting the thread while in the wet condition to the caustic of a mercerization bath simultaneously to mercerize said thread and to deposit silica in the fibers thereof.
- the method of producing a cellulosic thread having improved properties comprising the steps of treating said thread with a solution containing 1% by weight of caustic and about 0.1 to 5.0% by weight of a wetting agent having the formula then rinsing said thread with water at about F. to remove the caustic from the surface of the thread, next treating said thread with an aqueous dispersion of col loidal silica containing about 1% by Weight of silica, thereafter subjecting the thread while in the wet condition to the caustic of a mercerization bath simultaneously to mercerize said thread and to deposit silica in the fibers thereof.
- the method of producing a cellulosic thread having improved properties comprising the steps of treating said thread with a solution containing 1% by weight of caustic and about 0.1 to 5.0 %by weight of a wetting agent having the formula C H CH(C H )C H CH(SO Na)C H CH(C H then rinsing said thread with water at about 190 F. to remove the caustic from the surface of the thread, next treating said thread with an aqueous dispersion of colloidal silica containing about 1% by weight of silica at a pH of about 9.8, thereafter subjecting the thread while in the wet condition to the caustic of a mercerization bath simultaneously to mercerize said thread and to deposit silica on the fibers thereof.
- the method of producing a cellulosic thread having improved properties comprising the steps of wetting said thread with water at about 190 F., then treating said thread with an aqueous dispersion of colloidal silica having about 1% by weight of silica and about 0.1 to 5.0% by weight of said wetting agent, next treating said thread with a 1% caustic solution, thereafter subjecting said thread while in the Wet condition to the caustic of a mercerization bath simultaneously to mercerize said thread and deposit silica on the fibers thereof.
- the method of producing a cellulosic thread having improved properties comprising the steps of wetting said thread with Water at about 190 F. containing about 0.1 to 5.0% by weight of a wetting agent, then treating said thread with an aqueous dispersion of colloidal silica having about 1% by Weight of silica and about 0.1 to 5.0% by weight of said wetting agent, next treating said thread with a 1% caustic solution, thereafter subjecting said thread while in the wet condition to the caustic of a mercerization bath simultaneously to mercerize said thread and deposit silica on the fibers thereof.
- the method of producing a cellulosic thread having improved properties comprising the steps of wetting said thread with water at about 190 F. containing about 0.0 to 5.0% by weight of a wetting agent having the formula C H CH (C 15 C H CH (SO Na C H CH (C H then treating said thread with an aqueous dispersion of colloidal silica having about 1% by Weight of silica and about 0.1 to 5.0% by weight of said wetting agent, next treating said thread with a 1% caustic solution, there- 7 after subjecting said thread while in the wet condition to the caustic of a mercerization bath simultaneously to mercerize said thread and deposit silica on the fibers thereof.
- a wetting agent having the formula C H CH (C 15 C H CH (SO Na C H CH (C H then treating said thread with an aqueous dispersion of colloidal silica having about 1% by Weight of silica and about 0.1 to 5.0% by weight of said wetting agent, next treating said thread with a 1%
- the method of producing a cellulosic material having improved properties comprising the steps of treating said material with a solution containing about 0.1 to about 5.0% by weight of a salt selected from the group consisting of alkali metal salts of strong acids, alkali metal salts of weak acids, higher fatty amine salts, quaternary ammonium, sulfonium and phosphonium compounds, and alkali metal salts of ethylenediaminetetracarboxylic acids, then treating said material with an aqueous dispersion of colloidal silica, then subjecting said material while in the wet condition to the caustic of a mercerization bath simultaneously to mercerize said material and to deposit silica in the fibers thereof.
- a salt selected from the group consisting of alkali metal salts of strong acids, alkali metal salts of weak acids, higher fatty amine salts, quaternary ammonium, sulfonium and phosphonium compounds, and alkali metal salts of
- the method of producing a cellulosic material having improved properties comprising the steps of treating said material with an aqueous dispersion of colloidal silica, treating said material with a solution containing about 0.1 to about 5.0% by weight of a salt selected from the group consisting of alkali metal salts of strong acids,
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US154357A US3297399A (en) | 1961-11-22 | 1961-11-22 | Process of mercerizing a cellulosic material while simultaneously depositing silica thereon |
GB42604/62A GB996525A (en) | 1961-11-22 | 1962-11-12 | Improvements in the treatment of cotton yarns and threads |
DE19621419480 DE1419480A1 (de) | 1961-11-22 | 1962-11-19 | Cellulosehaltiges Fasermaterial und Verfahren zu seiner Herstellung |
FR915932A FR1339863A (fr) | 1961-11-22 | 1962-11-20 | Méthode de production des fils et filés textiles améliorés |
CH1378062A CH390216A (de) | 1961-11-22 | 1962-11-22 | Verfahren zur Verbesserung der Eigenschaften von Textilien aus Cellulosefasern und veredelte Textilien aus Cellulose |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US154357A US3297399A (en) | 1961-11-22 | 1961-11-22 | Process of mercerizing a cellulosic material while simultaneously depositing silica thereon |
Publications (1)
Publication Number | Publication Date |
---|---|
US3297399A true US3297399A (en) | 1967-01-10 |
Family
ID=22551036
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US154357A Expired - Lifetime US3297399A (en) | 1961-11-22 | 1961-11-22 | Process of mercerizing a cellulosic material while simultaneously depositing silica thereon |
Country Status (5)
Country | Link |
---|---|
US (1) | US3297399A (fr) |
CH (1) | CH390216A (fr) |
DE (1) | DE1419480A1 (fr) |
FR (1) | FR1339863A (fr) |
GB (1) | GB996525A (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4568349A (en) * | 1981-08-22 | 1986-02-04 | Sandoz Ltd. | Alkali treatment of cellulosic fiber goods |
US5254195A (en) * | 1992-05-08 | 1993-10-19 | Industrial Technology Research Institute | Process for manufacturing moisture exchange element |
WO2008031553A1 (fr) * | 2006-09-12 | 2008-03-20 | J. Rettenmaier & Söhne Gmbh + Co. Kg | Auxiliaire de filtrage et de traitement en fibres organiques |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US133101A (en) * | 1872-11-19 | Improvement in graphitized materials for journals, bearings, and other purposes | ||
US596464A (en) * | 1897-12-28 | On - the - main | ||
GB338654A (en) * | 1929-09-23 | 1930-11-27 | Robert Walker Rannie Mackenzie | Improvements in and relating to the filling, loading or weighting of cotton, linen and other woven cellulosic fabrics |
US1839168A (en) * | 1928-12-20 | 1931-12-29 | Drager Otto H | Fabric for gas protection masks or the like and method for producing same |
US2104748A (en) * | 1934-02-28 | 1938-01-11 | Sayles Finishing Plants Inc | Crisp sheer fabrics and process of making same |
US2497519A (en) * | 1946-12-04 | 1950-02-14 | Alrose Chemical Company | Art of stabilizing rayon type fabric |
US2582590A (en) * | 1946-08-15 | 1952-01-15 | Armour Res Found | Method of making magnetic material |
US3013898A (en) * | 1958-09-19 | 1961-12-19 | Du Pont | Coating painted surfaces with a silica sol |
-
1961
- 1961-11-22 US US154357A patent/US3297399A/en not_active Expired - Lifetime
-
1962
- 1962-11-12 GB GB42604/62A patent/GB996525A/en not_active Expired
- 1962-11-19 DE DE19621419480 patent/DE1419480A1/de active Pending
- 1962-11-20 FR FR915932A patent/FR1339863A/fr not_active Expired
- 1962-11-22 CH CH1378062A patent/CH390216A/de unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US133101A (en) * | 1872-11-19 | Improvement in graphitized materials for journals, bearings, and other purposes | ||
US596464A (en) * | 1897-12-28 | On - the - main | ||
US1839168A (en) * | 1928-12-20 | 1931-12-29 | Drager Otto H | Fabric for gas protection masks or the like and method for producing same |
GB338654A (en) * | 1929-09-23 | 1930-11-27 | Robert Walker Rannie Mackenzie | Improvements in and relating to the filling, loading or weighting of cotton, linen and other woven cellulosic fabrics |
US2104748A (en) * | 1934-02-28 | 1938-01-11 | Sayles Finishing Plants Inc | Crisp sheer fabrics and process of making same |
US2582590A (en) * | 1946-08-15 | 1952-01-15 | Armour Res Found | Method of making magnetic material |
US2497519A (en) * | 1946-12-04 | 1950-02-14 | Alrose Chemical Company | Art of stabilizing rayon type fabric |
US3013898A (en) * | 1958-09-19 | 1961-12-19 | Du Pont | Coating painted surfaces with a silica sol |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4568349A (en) * | 1981-08-22 | 1986-02-04 | Sandoz Ltd. | Alkali treatment of cellulosic fiber goods |
US5254195A (en) * | 1992-05-08 | 1993-10-19 | Industrial Technology Research Institute | Process for manufacturing moisture exchange element |
WO2008031553A1 (fr) * | 2006-09-12 | 2008-03-20 | J. Rettenmaier & Söhne Gmbh + Co. Kg | Auxiliaire de filtrage et de traitement en fibres organiques |
Also Published As
Publication number | Publication date |
---|---|
CH1378062A4 (fr) | 1964-12-31 |
CH390216A (de) | 1965-07-30 |
FR1339863A (fr) | 1963-10-11 |
GB996525A (en) | 1965-06-30 |
DE1419480A1 (de) | 1969-04-17 |
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