WO2016127951A1 - Process and device for chlorine-free shrinkproof treatment of wool raw material and article thereof - Google Patents
Process and device for chlorine-free shrinkproof treatment of wool raw material and article thereof Download PDFInfo
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- WO2016127951A1 WO2016127951A1 PCT/CN2016/073835 CN2016073835W WO2016127951A1 WO 2016127951 A1 WO2016127951 A1 WO 2016127951A1 CN 2016073835 W CN2016073835 W CN 2016073835W WO 2016127951 A1 WO2016127951 A1 WO 2016127951A1
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- Prior art keywords
- wool
- treatment
- chlorine
- free
- product
- Prior art date
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- 210000002268 wool Anatomy 0.000 title claims abstract description 422
- 238000011282 treatment Methods 0.000 title claims abstract description 314
- 238000000034 method Methods 0.000 title claims abstract description 122
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- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims abstract description 71
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- 238000005406 washing Methods 0.000 claims abstract description 41
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 37
- -1 phosphine compound Chemical class 0.000 claims abstract description 30
- 230000002779 inactivation Effects 0.000 claims abstract description 28
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- 238000001035 drying Methods 0.000 claims abstract description 18
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- 239000007788 liquid Substances 0.000 claims description 123
- 239000003795 chemical substances by application Substances 0.000 claims description 50
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- 229910017053 inorganic salt Inorganic materials 0.000 claims description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 13
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- YICAEXQYKBMDNH-UHFFFAOYSA-N 3-[bis(3-hydroxypropyl)phosphanyl]propan-1-ol Chemical compound OCCCP(CCCO)CCCO YICAEXQYKBMDNH-UHFFFAOYSA-N 0.000 claims description 11
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 11
- 239000010410 layer Substances 0.000 claims description 11
- 230000009471 action Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XVBMSIOVPSSTBM-UHFFFAOYSA-N 4-[bis(3-carboxypropyl)phosphanyl]butanoic acid Chemical compound OC(=O)CCCP(CCCC(O)=O)CCCC(O)=O XVBMSIOVPSSTBM-UHFFFAOYSA-N 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- PZIJUXHDLWNNRW-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)phosphanyl]ethanol Chemical compound OCCP(CCO)CCO PZIJUXHDLWNNRW-UHFFFAOYSA-N 0.000 claims description 8
- 108091005507 Neutral proteases Proteins 0.000 claims description 8
- 102000035092 Neutral proteases Human genes 0.000 claims description 8
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- 238000010998 test method Methods 0.000 claims description 8
- CRHOVAVWTLRGNY-UHFFFAOYSA-N 5-[bis(4-carboxybutyl)phosphanyl]pentanoic acid Chemical compound OC(=O)CCCCP(CCCCC(O)=O)CCCCC(O)=O CRHOVAVWTLRGNY-UHFFFAOYSA-N 0.000 claims description 7
- 230000000415 inactivating effect Effects 0.000 claims description 7
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- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
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- 125000004185 ester group Chemical group 0.000 claims description 4
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- 238000001764 infiltration Methods 0.000 claims description 4
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- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 210000000085 cashmere Anatomy 0.000 claims description 3
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- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
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- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 claims 1
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- 238000010924 continuous production Methods 0.000 description 7
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- 150000004045 organic chlorine compounds Chemical class 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- 230000007246 mechanism Effects 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229920013822 aminosilicone Polymers 0.000 description 2
- 239000012753 anti-shrinkage agent Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229920000136 polysorbate Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- RQQIRJISLWXIOA-UHFFFAOYSA-N 5-phosphanylpentanoic acid Chemical compound OC(=O)CCCCP RQQIRJISLWXIOA-UHFFFAOYSA-N 0.000 description 1
- 241000194108 Bacillus licheniformis Species 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- 125000005865 C2-C10alkynyl group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- FSNCEEGOMTYXKY-JTQLQIEISA-N Lycoperodine 1 Natural products N1C2=CC=CC=C2C2=C1CN[C@H](C(=O)O)C2 FSNCEEGOMTYXKY-JTQLQIEISA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
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- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
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- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
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- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
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- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- SSILHZFTFWOUJR-UHFFFAOYSA-N hexadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCS(O)(=O)=O SSILHZFTFWOUJR-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 108010009355 microbial metalloproteinases Proteins 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 239000011265 semifinished product Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
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- 239000001488 sodium phosphate Substances 0.000 description 1
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- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- LEAHFJQFYSDGGP-UHFFFAOYSA-K trisodium;dihydrogen phosphate;hydrogen phosphate Chemical compound [Na+].[Na+].[Na+].OP(O)([O-])=O.OP([O-])([O-])=O LEAHFJQFYSDGGP-UHFFFAOYSA-K 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
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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
- 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
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- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
- D06L1/16—Multi-step processes
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- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B9/00—Solvent-treatment of textile materials
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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
- D06M11/11—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
- D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
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- 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
- D06M13/52—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment combined with mechanical treatment
- D06M13/522—Fulling
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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
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B21/00—Successive treatments of textile materials by liquids, gases or vapours
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
- D06B3/10—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics
- D06B3/18—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics combined with squeezing, e.g. in padding machines
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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
- 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
- D06M2101/10—Animal fibres
- D06M2101/12—Keratin fibres or silk
-
- 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
- D06M2200/45—Shrinking resistance, anti-felting properties
Definitions
- the invention relates to the field of wool product processing, in particular to a chlorine-free shrink-proof treatment process and equipment for wool raw materials and products, in particular to a continuous processing technology and equipment for anti-shrinkage treatment of chlorine-free wool strips and wool products.
- Wool is an important raw material for the textile industry. It has many excellent properties such as good elasticity, strong hygroscopicity, non-staining, good warmth and soft gloss.
- wool is attached with a layer of scales which are mainly composed of keratin proteins and overlap each other. Because of the different friction coefficients in the direction of the scales, the wool fibers will interpenetrate under the repeated action of external force. Entangled, woven, felted and shriveled.
- the fleece has the advantages of beautiful appearance, rich hand feeling softness and good warmth performance, it also makes the wool fabric easy to cause dimensional shrinkage and deformation during the washing process. Therefore, in order to improve the anti-felting performance of the wool textile, in order to improve the dimensional stability of the wool fabric product, the product can achieve the "machine washable" effect, and the surface scale modification of the wool fiber is required from the source.
- the main methods for the modification and shrinkage treatment of wool surface scales are: chlorination method, covering method, protease method and the like.
- the most widely used is the organic halide AOX (which is an absorbable organic halide) produced during the chlorination process, which can seriously pollute the environment.
- Chinese patent CN201010605809.9 reported that the method of anti-shrinking and scaling of wool tops by adding potassium permanganate and DCCA as a catalyst to clean water and then introducing chlorine gas, the chlorine gas consumption is reduced on the original basis. 30%. Although this method has improved the traditional chlorination method, it still uses chlorine gas, which still causes serious environmental pollution.
- the covering method reduces the surface friction effect of the fiber by depositing a resin film on the surface of the wool to fill the gaps on the surface of the wool to smooth the surface of the wool. Although this treatment method can improve the felting property of the fiber to some extent, it will seriously affect the hand feeling of the wool fabric, and there is a general lack of durability.
- the protease method utilizes the hydrolysis of macromolecular peptide bonds on the surface of wool fibers by protease to partially dissolve the scales and cell membrane complexes of the wool, thereby achieving the purpose of partially or completely removing the scales.
- the treatment method has the advantages of mild treatment conditions, energy conservation and pollution reduction, and is an environmentally friendly wool anti-felting finishing method.
- the anti-shrinking effect of the treatment of wool by protease alone cannot meet the actual needs at present. Therefore, many of the wools must be pre-treated with proteases for biological modification (for example, with strong oxidizing agent permanganic acid). Potassium or the like is pre-oxidized or pretreated with a chloride solvent). All of the above pretreatment methods have disadvantages such as excessive treatment time, easy deactivation of the enzyme, and difficulty in controlling the treatment conditions.
- the object of the present invention is to provide a wool shrink-proof treatment process which is environmentally friendly, simple and easy to control, has a long anti-felting effect, and has high processing efficiency (or rapid) and is suitable for mass production.
- a shrinkage preventing agent for a chlorine-free shrinkage preventing treatment comprising: (a) an optional solvent; (b) a protease; and (c) An organophosphine compound represented by A and optionally an inorganic salt;
- each X is independently selected from the group consisting of a substituted or unsubstituted C1-C10 hydrocarbon group, wherein said substitution has one or more substituents selected from the group consisting of -OH, -COOH (carboxyl), C2-C8 ester group, -SH, -CN, C1-C3 alkyl group, C1-C3 alkoxy group;
- At least one X is a substituted C1-C10 hydrocarbon group having a -OH or COOH substituent
- the weight ratio of the protease to the organophosphine compound is 0.2-10:0.5-20;
- protease in the anti-shrinkage treatment agent is selected from the group consisting of a neutral protease, an alkaline protease, or a combination thereof.
- the chlorine-free treatment comprises descaling/anti-shrinking the wool material and/or the wool product.
- the wool material comprises a wool strip.
- the weight ratio of the protease to the organophosphine compound is from 0.5 to 5: 1-10; more preferably from 1 to 5: 1-10.
- the shrink prevention treatment agent further contains a basic compound.
- the basic compound is selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydrogencarbonates, alkaline earth metals. Bicarbonate, or a combination thereof.
- the basic compound is selected from the group consisting of NaOH, KOH, Ca(OH) 2 , Na 2 CO 3 , K 2 CO 3 , or a combination thereof.
- the "chlorine-free" means that the shrink-proof treatment agent does not contain an organochlorine compound, and does not include a hypochlorous acid compound selected from the group consisting of a compound containing a ClO - ion (root). may be generated ClO - ion compound (e.g., chlorine).
- the content of the hypochlorous acid compound is ⁇ 0.05% by weight, preferably ⁇ 0.01% by weight, more preferably ⁇ 0.001% by weight, most preferably About 0.
- the anti-shrinkage treatment agent is in a liquid state (i.e., a treatment liquid).
- the solvent is selected from the group consisting of water or an aqueous solvent.
- the anti-shrinkage treatment agent is a solid, semi-solid, and can be reconstituted as a treatment liquid by adding a solvent such as water at the time of application.
- the concentration of the organic phosphine compound is 1-10 g/L, preferably 1.5-10 g/L, more preferably 5- 10g/L.
- the concentration of the protease in the treatment liquid (or the reconstituted treatment liquid) is 0.1-25 g/L, preferably 0.2-10 g/L, more preferably 0.5-5 g/ L.
- the concentration of the inorganic salt in the treatment liquid (or the reconstituted treatment liquid) is 0.01 to 10 g/L, preferably 0.05 to 5 g/L, more preferably 0.1 to 2 g/L.
- the two Xs are the same.
- the three Xs are the same.
- the three Xs are different.
- each X is independently selected from the group consisting of a substituted or unsubstituted C1-C6 hydrocarbon group.
- the C1-C10 hydrocarbon group includes a C1-C10 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, and a C3-C8 cycloalkyl group.
- the C1-C10 hydrocarbon group includes a C1-C10 alkyl group and a C3-C8 cycloalkyl group.
- the anti-shrinkage treatment agent contains one or more components selected from the group consisting of a protease, an organic phosphine compound, an inorganic salt, and a surfactant, the contents thereof are as follows:
- the amount (wt) of the protease in the anti-shrinkage treatment agent is less than or equal to ( ⁇ ) the amount (wt) of the organophosphine compound.
- the pH thereof is 6.5-12, preferably 7-11.5, more preferably 7.5-10.5.
- the protease is an alkaline protease.
- the organophosphine compound is a water-soluble aliphatic organophosphine compound.
- the water solubility means that the solubility of the organophosphine compound in 100 g of water at 25 ° C is ⁇ 0.1 g, preferably ⁇ 0.5 g, more preferably ⁇ 2 g, such as 0.1-10 g or 0.5-5 g. .
- the organophosphine compound has the formula:
- R 1 is a substituted or unsubstituted C 2 -C 8 alkylene group (preferably a C 1 -C 6 alkylene group); and/or
- R 2 is selected from the group consisting of -OH, -COOH, or a C2-C8 ester group, an alkali metal, or an alkaline earth metal.
- R 1 is an unsubstituted C1-C6 alkylene group
- R 2 is selected from the group consisting of -OH, and -COOH.
- R 1 is selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, or a combination thereof.
- the aliphatic organophosphine compound is selected from the group consisting of tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, and tri (4-carboxybutyl)phosphine, or a combination thereof.
- the inorganic salt is selected from the group consisting of a Ca salt, a Mg salt, a Na salt, a Zn salt, an Al salt, a Ba salt, or a combination thereof.
- the inorganic salt is selected from the group consisting of hydrochloride, sulfate, carbonate, hydrogencarbonate, nitrate, nitrite, phosphate, monohydrogen phosphate, dihydrogen phosphate. Salt or a combination thereof.
- the inorganic salt is selected from the group consisting of Mg(NO 3 ) 2 , sodium phosphate, calcium hydrogen phosphate, CaCl 2 , or a combination thereof.
- the surfactant is selected from the group consisting of a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a combination thereof.
- the anti-shrinkage treatment agent further contains a pH buffer.
- the pH buffering agent is present in an amount of from 0.1 to 10 g/, preferably from 0.2 to 5 g/L.
- the pH buffer is selected from the group consisting of: disodium hydrogen phosphate - sodium dihydrogen phosphate buffer (PBS), NaHCO 3 -Na 2 CO 3 buffer, or combinations thereof.
- the shrink prevention treatment agent is in a liquid state at 25 to 80 °C.
- the shrink prevention treatment agent is liquid at a temperature of from 30 to 70 ° C, preferably from 40 to 60 ° C, more preferably from 45 to 55 ° C.
- the processed top is of a size of 10-30 g/m/feet, preferably 20-25 g/m/feet.
- n tops are simultaneously processed in parallel, wherein n is 10-100, 20-70, preferably 30-60.
- a shrink-proof treatment apparatus for a chlorine-free wool strip or a wool product comprising:
- a multiple padding apparatus comprising n independent, continuously arranged padders, each of the paddings comprising a soaking tank and a rolling roll, wherein the soaking tank is used for placing chlorine-free The shrink-treated shrink-proof treatment liquid so that the wool strip or wool product to be treated is immersed in the treatment liquid; and the rolling roll is used for rolling the soaked wool strip or wool product, and is subjected to an upstream rolling roll After the rolling, the wool strip or the wool product is sequentially entered into the soaking tank and the rolling roll of the downstream padder, thereby repeating the soaking and rolling treatment, wherein n is a positive integer of 2-20;
- a water washing device for washing the padded tops or wool products to form a washed top or wool product
- An optional softening device for softening the enzyme-inactivated tops or wool products to form a softened top or wool product
- An optional dryer for drying the softened tops or wool products obtained in the previous step is an optional dryer for drying the softened tops or wool products obtained in the previous step.
- a method for preventing shrinkage of a chlorine-free wool strip or a wool product comprising the steps of:
- n-padding treatment on the chlorine-free wool strip or wool product to be treated with the anti-shrinkage treatment agent, thereby obtaining a padded wool product, wherein n is a positive integer of 2-20;
- n is a positive integer of 3-10.
- treatment may be additionally carried out with a treatment liquid containing only the protease but no the organophosphine compound during and/or after the n-padding treatment.
- the total time T of the padding treatment of the step (b) is ⁇ 15 minutes, preferably ⁇ 10 minutes, more preferably ⁇ 5 minutes, most preferably ⁇ 3 minutes.
- the chlorine-free wool strip or wool article to be treated in step (a) is planarized.
- composition of the wool strip is selected from the group consisting of wool, cashmere, or a combination thereof.
- the wool strip has a size of from 40 to 150, preferably from 40 to 120, more preferably from 56 to 100.
- the temperature of the wetting/rolling operation is 5 to 80 ° C, preferably 10 to 60 ° C, more preferably 25 to 50 ° C, optimally 40. -50 ° C.
- the total time of the wetting/rolling operation is not particularly limited and is usually from 1 to 20 minutes, preferably from 1 to 10 minutes, more preferably 1 -5 minutes.
- the water washing temperature is not particularly limited, and is usually 5 to 60 ° C, preferably 10 to 50 ° C, more preferably 20 to 40 ° C, most preferably 20 to 30. °C.
- the washing time is not particularly limited in the step (c), and is usually from 30 seconds to 120 minutes, preferably from 1 minute to 60 minutes, more preferably from 2 to 30 minutes.
- the enzyme inactivation operation can employ conventional inactivation conditions as long as the residual protease is inactivated or substantially inactivated.
- no hypochlorous acid compound is used.
- the weight ratio of the volume of the shrink-proof treatment liquid to the wool product to be treated is not particularly limited as long as the top or wool product to be treated can be infiltrated.
- the number of times of padding may be the same or different, preferably the same.
- the number of times of padding is 3-15 times, preferably 4-12 times, more preferably 5-10 times.
- the treatment time of the padding in step 2) is from 3 to 1000 s, preferably from 5 to 800 s, more preferably from 8 to 600 s, most preferably from 10 to 300 s.
- the obtained padded wool product obtained in the step 2) has a liquid ratio of 50 to 160% by weight, preferably 60 to 150% by weight, more preferably 80 to 140% by weight.
- step 2) is repeated before step 3), the number of repetitions being 3-15 times, preferably 4-12 times, more preferably 5-10 times.
- the method before each step 2) is repeated, the method further comprises the step of: replacing the shrink-proof treatment liquid.
- the water for washing is at a temperature of 10 to 40 ° C, preferably 20 to 30 ° C.
- the water for washing with water has a pH of from 6.5 to 7.5, preferably 7.
- step 3 the padded wool product obtained in step 2) is washed with a quantity of water.
- the number of times of washing in step 3) is from 1 to 6 times, preferably from 2 to 4 times.
- the water washing time of the step 3) is from 1 to 60 minutes, preferably from 1 to 30 minutes, more preferably from 1 to 10 minutes.
- step 3) is repeated, the number of repetitions is 1-6 times. Preferably 2-4 times.
- step 4 the inactivation treatment is performed in a manner selected from the group consisting of hot water inactivation, hydrogen peroxide (H 2 O 2 ) inactivation, or a combination thereof.
- the hot water used for hot water inactivation has a temperature of from 85 to 100 ° C, preferably from 90 to 98 ° C, more preferably from 92 to 96 ° C.
- the treatment time for hot water inactivation is from 5 to 300 s, preferably from 8 to 200 s, more preferably from 10 to 100 s.
- the treatment time of the hydrogen peroxide inactivation treatment is 5 to 300 s, preferably 8 to 200 s, more preferably 10 to 100 s.
- step 4 the following steps are optionally further included after step 4):
- step 5) softening the product obtained in step 4) to obtain the desired wool product
- the softening treatment of step 5) is to soak the product obtained in step 4) with a softening agent.
- step 5 the ratio of the amount of the product obtained in step 4) to the softening agent is a conventional ratio.
- the soaking time of the softening treatment in the treatment agent in the step 5) is from 5 to 200 s, preferably from 8 to 100 s, more preferably from 10 to 50 s.
- the number of times of the softening treatment in the step 5) is 1-10 times, preferably 2-5 times, more preferably 3-4 times.
- the temperature of the treating agent used in the softening treatment in the step 5) is from 25 to 65 ° C, preferably from 30 to 50 ° C.
- the pH of the treatment agent used in the softening step of step 5) is from 5 to 8, preferably from 5.5 to 7.5.
- the softening treatment used in the step 5) has a concentration of the treatment agent of 5 to 100 g/L, preferably 10 to 50 g/L, more preferably 15 to 30 g/L.
- the treatment agent used in the softening treatment of step 5 is selected from the group consisting of wool smoothing agents, wool softening agents, or combinations thereof.
- the drying treatment in the step 6) has a treatment temperature of 60 to 100 ° C, preferably 70 to 90 ° C.
- the drying treatment time at the treatment temperature is from 1 to 30 minutes, preferably from 3 to 15 minutes.
- a shrink-proof, chlorine-free wool product which is free of residual organochlorine.
- the wool product is subjected to the shrink-proof treatment process (method) of the present invention. Anti-shrink processing.
- the wool product is subjected to a shrink-proof treatment using the chlorine-free wool strip or the anti-shrinkage treatment agent of the wool product described in the first aspect of the invention.
- the wool product is subjected to chlorine-free treatment using the shrink-proof treatment apparatus described in the second aspect of the invention.
- the scale layer removal rate of the wool surface layer in the treated chlorine-free wool product is 80-100%, preferably, compared to the wool product to be treated. It is 90-100%, more preferably 95-100%, such as 99-100%.
- the absolute value of the shrinkage of the treated chlorine-free wool product is ⁇ 10%, preferably ⁇ 8%, compared to the wool product to be treated. Preferably, it is ⁇ 6%, more preferably ⁇ 5%, and most preferably ⁇ 3%, wherein the measuring method is the International Wool Bureau TWC.TM31 test method,
- the strength of the treated chlorine-free wool product is maintained ⁇ 80%, preferably ⁇ 82%, more preferably than the wool product to be treated. ⁇ 84%.
- the elongation of the treated chlorine-free wool product remains ⁇ 70%, preferably ⁇ 75%, compared to the wool product to be treated.
- Good land ⁇ 80%.
- the treated chlorine-free wool product has a drip spread time of ⁇ 30 s, preferably ⁇ 15 s, more preferably ⁇ 10 s.
- the article comprises a top, a blanket, and a garment.
- a use of the anti-shrinkage treatment agent according to the first aspect of the invention which is used for chlorine-free shrink-proof treatment of tops or wool products.
- a non-chlorinated wool strip and a shrinkage preventing liquid for a wool product the main composition thereof being: a protease, a water-soluble aliphatic trisubstituted organic phosphine compound, an inorganic salt;
- the structure of the aliphatic trisubstituted organophosphine is: P-(RS) 3 , wherein R: is a hydrocarbon group having 1 to 6 carbons, and S is a hydroxyl group or a carboxyl group and a derivative thereof; the mass concentration thereof is 1 to 10 g/L;
- the inorganic salt is calcium chloride and its concentration is 0 to 2 g/L.
- the trisubstituted organophosphine is: tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, tris(4- At least one of carboxybutyl)phosphines.
- a continuous processing process for the anti-shrinkage treatment of a chlorine-free wool strip and a wool product comprising the steps of:
- Anti-shrinkage treatment the wool strips and wool products are leveled and transported through the rolls at a uniform speed into a plurality of anti-shrinkage treatment tanks alternately infiltrated and rolled 3-10 times.
- the process conditions are: the pH of the anti-shrinkage treatment liquid is 7 ⁇ 10.5, the temperature is 40 ⁇ 50°C; the rolling liquid rate is 60% ⁇ 150%; the process conveying speed is 3 ⁇ 15m/min, and the total infiltration and rolling time is 1-5 minutes;
- the inactivated wool strip is soaked in a tank of a conventional wool smoothing agent or a silicone softener, and subjected to a general softening treatment to improve the hand feeling of the wool fabric;
- the anti-shrinkage treatment liquid mainly comprises:
- Trisubstituted organophosphine at a concentration of 1 to 10 g/L
- the rest is water
- the trisubstituted organic phosphine is: tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, tris(4-carboxybutyl)phosphine At least one.
- the soaking and pressing or rolling are repeated 3-10 times; the total time of the soaking treatment is between 1 and 5 minutes; and the process conveying speed is 3-8 meters/minute.
- the wool strip is 56 to 100 pieces of wool or cashmere.
- FIG. 1 is a view showing the effect of stripping of wool fiber scales according to Example 1 of the present invention.
- Fig. 2 is a view showing the effect of stripping of wool fiber scales according to Example 2 of the present invention.
- Fig. 3 is a view showing the effect of stripping of wool fiber scales according to Example 3 of the present invention.
- Fig. 4 is a view showing the effect of stripping of wool fiber scales according to Example 4 of the present invention.
- Fig. 5 is a view showing the effect of stripping of wool fiber scales according to Example 5 of the present invention.
- Fig. 6 is a flow chart showing an example of a process of the present invention.
- FIG. 7 is a schematic illustration of a chlorine free processing apparatus of the present invention.
- the inventors After long-term and intensive research, the inventors have unexpectedly prepared a descaling and shrink-proof process for chlorine-free wool/wool products and corresponding shrink-proof treatment agents and equipment.
- the process and the shrink-proof treatment liquid of the invention can remove the scale layer on the surface of the wool fiber efficiently and quickly under the condition of no chlorine, and modify the scale layer to To improve the felting properties of wool products and improve product dimensional stability.
- the inventors completed the present invention.
- the present invention provides a continuous processing process for the anti-shrinkage treatment of chlorine-free wool strips and wool products.
- Including anti-shrinkage treatment, water washing, protease inactivation, soft treatment, dehydration, drying step, according to the characteristics of wool fiber is a protein fiber, the activator and metal salt of protease and water-soluble aliphatic tri-substituted organophosphine structure are selected.
- the high-efficiency integrated catalytic system composed of nonionic surfactant can synergistically and efficiently remove the scale layer on the surface of the wool fiber, and modify the scale layer to improve the felting performance of the wool product, improve the dimensional stability of the product, and make the fabric have Anti-pilling characteristics and smooth feel.
- the invention can completely replace the chlorination shrinkage prevention method in the prior art, avoids the environmental pollution caused by the chlorination method, is a clean type treatment process that meets environmental requirements, and has no problem of chlorination pollution.
- the method has the advantages of small dosage, low cost, simple process, low requirement on equipment, continuous operation, and industrial production.
- wool stock includes wool, tops, or semi-finished products that have not been scaled and shrunk.
- the term may also include wool raw materials that have not been fully descaled, although subjected to descaling shrinkage treatment.
- wool/wool As used herein, the terms “wool/wool”, “wool and/or wool” are used interchangeably and refer to a wool strip, or a wool article, or a combination of the two. The term may include both wool strands/wool articles to be treated, as well as wool strands/wool articles that are processed or treated.
- chlorine-free product of the invention As used herein, the terms "chlorine-free product of the invention", “chlorine-free wool strip/wool product of the invention” are used interchangeably and refer to wool/wool products obtained by the chlorine-free descaling shrink-proof treatment process of the present invention. . Since the chlorine-free descaling shrinkage prevention process of the present invention does not use an organochlorine compound and does not use a hypochlorous acid compound (i.e., a compound containing a ClO-ion or a compound which can generate a ClO-ion), it is safe. Excellent chlorine-free wool products (including wool/wool products).
- a hypochlorous acid compound i.e., a compound containing a ClO-ion or a compound which can generate a ClO-ion
- the shrink-proof treatment agent (or liquid) is used interchangeably and refers to a shrink-proof treatment agent (or liquid) of the chlorine-free wool wool/wool product of the present invention.
- the present invention provides a descaling anti-shrinkage treatment agent for the chlorine-free wool wool/wool product of the present invention.
- the descaling anti-shrinkage treatment agent of the present invention may be in a solid or liquid state.
- the anti-shrinkage treatment liquid of the corresponding chlorine-free wool wool/wool product can be reconstituted by adding water (or an aqueous solvent).
- the present invention wherein the various combinations may have been mixed together (i.e., present in a mixed manner), may also be present in a non-mixed manner, and may be formulated in situ upon use.
- the main components of the anti-shrinkage treatment liquid for a chlorine-free wool strip and a wool product are: a protease, a water-soluble aliphatic trisubstituted organic phosphine compound, an inorganic salt; and the water-soluble aliphatic tri-substituted organic
- the phosphine structure is: P-(RS) 3 , wherein R: is a hydrocarbon group having 1 to 6 carbons, S is a hydroxyl group or a carboxyl group and a derivative thereof; the mass concentration is 1 to 10 g/L; and the inorganic salt is calcium chloride. , its concentration is 0 ⁇ 2g / L.
- preferred trisubstituted organophosphines include, but are not limited to, tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, three (4-carboxybutyl)phosphine, or a combination thereof.
- the protease comprises a neutral protease, an alkaline protease, or a combination thereof.
- the neutral protease refers to a protease having a pH optimum of neutrality (e.g., about 6.8 to 7.0), and its molecular weight is generally 35 to 40 kD.
- Neutral proteases suitable for use in the present invention include neutral proteases which are commercially available or prepared by conventional methods, such as neutral proteases from microorganisms, Neutrase, or combinations thereof.
- the alkaline protease refers to a protease having an optimum pH of alkaline (e.g., about 9 to 11), and has a molecular weight of generally 26 to 34 kD.
- Alkaline proteases suitable for use in the present invention include alkaline proteases which are commercially available or prepared by conventional methods, such as alkaline protease from Bacillus licheniformis (molecular weight of about 27,300, which is a serine-type endoprotease), from Streptomyces. Alkaline protease, 2709 alkaline protease, Novo protease, Carsberg protease, and the like.
- the concentration of the protease is generally from 0.1 to 25 g/L, preferably from 0.2 to 10 g/L, more preferably from 0.5 to 5 g/L of the anti-shrinkage liquid.
- the amount (or concentration) of the protease is generally 1 ⁇ 10 4 - 1 ⁇ 10 8 U / L of anti-retraction liquid, preferably 5 ⁇ 10 4 - 5 ⁇ 10 7 U / L, in terms of International Units (IU). More preferably, it is 1 ⁇ 10 5 - 1 ⁇ 10 7 U / L.
- the shrink-proof treatment liquid of the present invention further contains a nonionic surfactant (e.g., JFC) or an anionic surfactant.
- nonionic surfactants include, but are not limited to, polyoxyethylene surfactants (eg, alkylphenol ethoxylates (APEO), fatty acid polyoxyethylene esters (AE), fatty acid methyl esters ethoxylates) A base compound (FMEE)), and a polyol type surfactant (such as sorbitan esters, including Tween and Span), or a combination thereof.
- polyoxyethylene surfactants eg, alkylphenol ethoxylates (APEO), fatty acid polyoxyethylene esters (AE), fatty acid methyl esters ethoxylates) A base compound (FMEE)
- a polyol type surfactant such as sorbitan esters, including Tween and Span
- Representative examples include: Tween, Span, JFC, or a combination thereof.
- anionic surfactants include, but are not limited to, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate (SDS), hexadecyl sulfonate, or combinations thereof.
- the concentration of the surfactant is from 0.001 to 1.0% by weight or from 0.01 to 10 g/L, preferably from 0.1 to 2 g/L.
- the pH of the shrink prevention treatment liquid of the present invention is from 7 to 10.5.
- the present invention provides a shrink-proof treatment liquid for a chlorine-free wool strip and a wool product, the main mass composition of which is:
- Trisubstituted organophosphine at a concentration of 1 to 10 g/L
- the rest is water.
- the anti-shrinkage treatment agent (liquid) of the present invention can directly process the wool strip/wool product, thereby obtaining a deburring and shrink-proof wool strip/wool product.
- the anti-shrinkage treatment liquid of the present invention does not contain an organochlorine compound, and does not use a hypochlorous acid compound (that is, a compound containing ClO- ions or can generate ClO- ions). a compound such as Cl 2 ).
- the organochlorine compound includes DCCA, chloroform, carbon tetrachloride, TCCA, and the like.
- the main components of the chlorine-free wool strip and the anti-shrinkage treatment liquid of the wool product of the present invention are a protease, a water-soluble aliphatic tri-substituted organic phosphine compound and an inorganic salt.
- water-soluble aliphatic trisubstituted organophosphine structure is: P-(RS) 3 ,
- R is a hydrocarbon group having 1 to 6 carbons (C), and S is a hydroxyl group (-OH) or a carboxyl group (-COOH) and a derivative thereof.
- the amount used is 1 g to 10 g/L; the inorganic salt is calcium chloride or the like, and the amount thereof is 0 g/L to 2 g/L.
- the trisubstituted organic phosphine is: tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, tris(4-carboxybutyl)phosphine At least one.
- the protease is a neutral protease, an alkaline protease or the like, and the protease has a concentration of 0.5 g/L to 5 g/L.
- the pH of the anti-shrinkage treatment liquid is 7 to 10.5.
- the main mass composition of the anti-shrinkage treatment liquid is:
- Trisubstituted organophosphine at a concentration of 1 to 10 g/L
- the rest is water.
- Anti-shrinkage treatment method for chlorine-free wool wool or wool products
- the invention also provides a shrink-proof treatment method for a chlorine-free wool strip or a wool product, wherein the wool strip/wool product is treated with the chlorine-free descaling anti-shrinkage treatment liquid of the invention, thereby obtaining excellent shrink-proof property.
- Wool strip/wool products It should be understood that although the shrink-proof treatment liquid and method of the present invention can sufficiently achieve descaling to obtain a fully descaled wool product, the method of the present invention can also be used to produce incomplete descaling (i.e., partial descaling, as needed). ) wool products.
- the present invention provides a continuous processing process for the anti-shrinkage treatment of chlorine-free wool strips and wool products, comprising the following steps:
- the wool strip/wool product is leveled and conveyed uniformly through the roll into one or more anti-shrinkage treatment tanks, alternately infiltrated and rolled (eg 3-10 times), process conditions
- the pressure of the anti-shrinkage treatment liquid is 7 to 10.5, and the temperature is 40 to 50 ° C; wherein, the total time of infiltration and rolling is 1 to 5 minutes;
- the wool strips are flattened side by side through a roll and fed into a plurality of anti-shrinkage treatment liquid tanks for alternately infiltrating and rolling (squeezing) pressure 3-10 times, the process condition is: the pH of the shrink-proof treatment liquid is 7 ⁇ 10.5, the temperature is 40 ⁇ 50 ° C; the rolling liquid rate is 60% ⁇ 150%; the process conveying speed is 3 ⁇ 15 m / min (preferably 3-8 m / min), the total infiltration and rolling time 1-5 minute;
- the washed wool strip is quickly passed through a 85-95 ° C hot water tank or a solution containing 0.1 to 1 g / liter of hydrogen peroxide to inactivate the protease that has not been completely washed;
- the inactivated wool strip is soaked in a tank of a conventional wool smoothing agent or a silicone softener, and subjected to a general softening treatment to improve the hand feeling of the wool fabric;
- the anti-shrinkage treatment liquid mainly comprises:
- Trisubstituted organophosphine at a concentration of 1 to 10 g/L
- the rest is water
- the trisubstituted organic phosphine is: tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, tris(4-carboxybutyl)phosphine At least one.
- the soaking and rolling operations can be repeated a plurality of times, for example, 3 to 10 times.
- the total time of the soaking and rolling treatment is not particularly limited and is usually from 0.5 to 20 minutes, preferably from 1 to 10 minutes, more preferably from 1 to 5 minutes.
- the present invention requires only a very short total time of the wetting/rolling operation because the chlorine-free descaling anti-shrinkage treatment agent of the present invention can perform descaling very efficiently and almost without damage.
- the chlorine-free shrink-proof treatment process of the present invention is continuous, wherein the conveying speed in the continuous process may be from 0.5 to 20 m/min, preferably from 1 to 10 m/min.
- the processing includes:
- Anti-shrinkage treatment The stripping treatment of the wool strip by the protease integrated catalytic system. In the case of no tension of each wool strip, the wool strips are flattened side by side through a roll and fed into a high-efficiency catalytic system consisting of protease, water-soluble aliphatic trisubstituted organophosphorus bioenzyme activator and inorganic salt catalyst.
- the nonionic surfactant acts as an auxiliary penetrant, the pH is 7 ⁇ 10.5, the temperature of the catalytic system is 40-50 °C, and the wool strip is completely saturated (the soaking can be accelerated by the suction roller and the exchange speed of the wool fiber and the surrounding treatment liquid) ), the wool strip is extruded by a roll action, and the liquid ratio is 60% to 150%. After that, it is again transferred into a catalytic system with a temperature of 40 to 50 ° C. After soaking, the wool strip is pressed by the action of the rolls, so that the padding is repeated, and the speed of the process is controlled at 3 to 15 m/min (optional 3-8 m). /min), according to the wool count and product quality requirements, in the same integrated catalytic system treatment liquid and the same treatment conditions, after 1 to 5 minutes and after 3 to 10 times of padding, and finally transmitted to the subsequent correlation Process the tank for continuous automation.
- the second step of the washed wool strip is evenly and quickly passed through the boiling water tank or contains A solution of 0 to 1 g/L of hydrogen peroxide. Inactivate the protease that has not been completely washed away.
- Soft treatment Soaking the inactivated wool strips in a conventional wool smoothing agent or silicone softener (ie, in a tank softening treatment, a general softening treatment, the softening agent is a hydrogen-containing silicone oil, an amino silicone oil, and a modified silicone oil or their Emulsion) to improve the feel of wool fabrics.
- a conventional wool smoothing agent or silicone softener ie, in a tank softening treatment, a general softening treatment, the softening agent is a hydrogen-containing silicone oil, an amino silicone oil, and a modified silicone oil or their Emulsion
- the invention also provides a chlorine free processing apparatus for use in the method of the invention.
- a typical processing device is shown in Figure 7.
- the device includes:
- a multiple padding apparatus 10 comprising n independent, continuously arranged padders (not shown), each of the paddings comprising a soaking tank and a rolling roll, wherein the soaking tank a shrink-proof treatment liquid for placing a chlorine-free shrink-proof treatment, so that the wool wool or wool product to be treated is immersed in the treatment liquid; and the rolling roller is used for rolling the soaked wool wool or wool product And the wool strip or wool product after being rolled by the upstream rolling roll is sequentially entered into the soaking tank and the rolling roll of the downstream padder, thereby repeating the soaking and rolling treatment, wherein n is a positive integer of 2-20;
- a water washing device 20 for washing the padded tops or wool products to form a washed top or wool product
- An optional dryer 50 for drying the softened tops or wool products obtained in the previous step is optional.
- the multiple padding device, the water washing device, the enzyme inactivation device, the optional soft processing device, and the optional dryer are sequentially arranged.
- one or more auxiliary padding devices are further provided between or after each of the padding devices of the multiple padding device, and each of the auxiliary padding devices independently includes an auxiliary soaking tank. And an auxiliary rolling roll, wherein the auxiliary soaking tank is provided with a protease treatment solution containing no organic phosphine compound, and/or a protease-free organic phosphine compound treatment liquid.
- the auxiliary soaking tank is an enzyme processing tank.
- the enzyme treatment tank is located after the second, third, fourth or fifth padder.
- n 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, preferably
- the ground is 3-15, more preferably 4-10.
- each of the paddles may be the same or different.
- each of the padders is sequentially arranged.
- the anti-shrinking treatment agent (or liquid) according to the first aspect of the invention is contained in the soaking tank.
- the soaking tank is a suction drum washing tank.
- the soaking tank is independently provided with or without a heating device or a temperature controlling device.
- each of the heating device or the temperature control device controls the temperature range to 25-80 ° C, preferably 30-70 ° C, more preferably 40-60 ° C, and most preferably 45-55. °C.
- the water washing apparatus comprises m water washers, wherein m is a positive integer of 1-10, preferably 1-6, preferably 2-4.
- each of the water washers contains solvent water.
- the temperature of the solvent water in each of the water washers is 10 to 40 ° C, preferably 20 to 30 ° C.
- the pH of the solvent water in each of the water washers is from 6.5 to 7.5, preferably from pH 7 to 0.2.
- the enzyme inactivating device is a high temperature inactivation tank and/or a hydrogen peroxide inactivation tank.
- the solvent water in the enzyme inactivating device has a temperature of from 85 to 100 ° C, preferably from 90 to 98 ° C, more preferably from 92 to 96 ° C.
- the enzyme inactivating device contains a solution containing H 2 O 2 .
- the concentration of the H 2 O 2 in the solution contained in the enzyme inactivating device is 0.01-50 g/L, preferably 0.05-30 g/L, more preferably 0.1-10 g/L.
- the soft treatment device contains a softening agent selected from the group consisting of a wool smoothing agent, a wool softening agent, or a combination thereof.
- the concentration of the softening agent is from about 1 to 50 g/L, preferably from 2 to 40 g/L, more preferably from 5 to 25 g/L.
- the wool softener comprises: a silicone-based softener.
- the silicone-based softener is selected from the group consisting of silicone oil, hydrogen silicone oil, amino silicone oil, modified silicone oil, or a combination thereof.
- the present invention also provides a shrink-proof, chlorine-free wool/wool product obtained with the chlorine-free shrink-proof treatment process of the present invention with little or no residual organic chlorine.
- ecoshine or "ecoshine product” refers to a non-chlorinated chlorine-free product obtained with the chlorine-free shrink-proof treatment process of the present invention with little or no residual organic chlorine. Wool strip/wool products.
- the chlorine-free tops or wool products of the present invention i.e., Evexin products
- have excellent properties including, but not limited to:
- the scale layer removal rate of the wool surface layer in the treated wool product is 80-100%, preferably 90-100%, more preferably, compared to the wool product to be treated. 95-100%, such as 99-100%.
- (b) low shrinkage ratio the absolute value of the shrinkage of the treated wool product is ⁇ 10%, preferably ⁇ 8%, preferably ⁇ 6%, more preferably ⁇ 5, compared to the wool product to be treated. %, optimally ⁇ 3%, wherein the measurement method is the International Wool Bureau TWC.TM31 test method.
- the inventors have found that there are some special structures and substances in the scale layer on the surface of the wool, such as cystine and lipids containing disulfide bonds, so that it is difficult for the protease to effectively digest and decompose the surface layer of the scale and the high-sulfur protein therein.
- the multiple padding process of the present invention can effectively change the structure of the scale layer on the surface of the wool, so that proteins such as high sulfur proteins are more easily degraded by proteases, and the other is In terms of maintaining or increasing the viability of the protease, the scaling and shrinkage of the wool can be achieved extremely efficiently and quickly.
- the action of the protease is mainly to degrade the scales on the surface of the wool fiber by hydrolysis; the water-soluble aliphatic trisubstituted organophosphine is rapidly reduced on the one hand by its unique action on the disulfide bond in the wool.
- the presence of a large number of disulfide bonds and activation of the reaction substrate facilitates the reaction of the protease with the wool macromolecule.
- it has a good stabilizing effect on the activity of the protease, and can effectively reduce the decrease of the protease activity in the integrated catalytic system.
- the catalytic action of the protease can be further activated, thereby producing a rapid reaction effect.
- the main function of the inorganic salt catalyst is to further activate the protease; and the main function of the surfactant is to assist the treatment liquid to wet and penetrate as soon as possible on the surface of the wool fiber.
- multiple padding or repeated padding is also a necessary condition for achieving a rapid process in the present invention.
- the rapid contact and action of the protease and the activator with the surface of the wool fiber are forcibly achieved, and the reactants and the hydrolyzed product are also cleaned, which is beneficial to the further progress of the reaction.
- the present invention has the following main advantages:
- the invention adopts a high-efficiency catalytic system mainly composed of a protease and a water-soluble organic phosphine structure activator as a treatment liquid to sort the wool, and utilizes the synergistic action of the two to achieve continuous processing of the chlorine-free wool filament light shrinkage prevention process, and the process does not occur during the processing.
- Toxic and harmful substances fundamentally solve the pollution of chlorinated mercerizing to the environment, in line with the concept of "ecological textile", will not cause environmental pollution
- the process of the invention has low requirements on equipment, can be continuously operated, and is beneficial to realize industrial production.
- the treatment liquid of the present invention is prepared by weighing a protease, a water-soluble aliphatic trisubstituted organic phosphine compound, an inorganic salt and a surfactant according to a main formula, and is prepared by a general mass concentration (g/L) preparation method.
- the organic phosphine compounds used were all purchased from Tianjin Binhai Oriental Technology Co., Ltd.
- the wool strip is subjected to a chlorine-free shrink-proof treatment by a continuous process of five-fold padding.
- the tank is a suction drum (type) washing tank (general device) having a width of 1 m and a volume of 360 liters and having a circumference of one meter.
- the suction drum tank has an automatic heating device (general device), and the main component is Highly efficient catalytic solution of alkaline protease 3g/L, tris(3-hydroxypropyl)phosphine 3g/L (addition of nonionic surfactant JFC 1g/L), pH 9 (disodium hydrogen phosphate and Sodium dihydrogen phosphate is a pH adjuster and the temperature is controlled at 50 °C.
- the wool wool strips are evenly laid flat on the top rollers and fed into the treatment liquid at a speed of 8 m/min to completely wet the wool strips, ensuring that each fiber in the wool strips is evenly and thoroughly treated;
- the pressure roller pressurizes the wool strip to ensure that the wool strip is about 135%; then the wool strip with the enzyme liquid is passed to the second treatment tank at a speed of 8 meters per minute. It took 15 seconds from the start of the wool strip to the first tank treatment liquid to the entry into the second tank treatment liquid.
- Second tank padding treatment liquid. Same as the first slot.
- Third tank padding treatment liquid. Same as the first slot.
- Fourth tank padding treatment liquid. Same as the first slot.
- the sixth tank washed.
- the wool strip is rolled and rolled to clean the reagents, enzymes and degradation products attached to the surface of the wool fiber, and the water temperature is normal temperature and the pH is 7.0.
- Seventh tank secondary washing. Same as the sixth slot.
- the eighth tank high-temperature water washing, play an enzyme inactivation, to prevent subsequent erosion of wool fiber, temperature 95 ° C, time 15 seconds.
- the ninth trough the conventional soft treatment, softening the wool fiber to achieve a soft effect and improve the hand feeling.
- the wool strip is then subjected to conventional dewatering and drying (for example, drying process conditions: drying temperature 70-90 ° C, drying time 3-10 minutes).
- the speed of the process is 8 m/min, and the treatment liquid is mixed for 5 times.
- the scale stripping effect of wool fiber treated by this process is shown in Fig. 1.
- the wool treated by this process maintained a strength of 85% and an elongation of 83% compared with that before treatment.
- the 5 ⁇ 5A test result is: -4.86%.
- the chlorine content of the treated wool was examined, and as a result, no residual chlorine component (organic matter) was detected.
- the wool strip is subjected to a chlorine-free shrink-proof treatment by a continuous process of six-fold padding.
- the tank is a suction drum tank having a width of 1 meter, a volume of 360 liters and a circumference of one meter.
- the suction drum tank has an automatic heating device containing alkaline protease 3g/L and tris (3-hydroxypropyl group).
- alkaline protease 3g/L and tris (3-hydroxypropyl group).
- the wool tops are evenly laid flat on the top rollers and fed into the treatment liquid at a speed of 3.8 m/min to completely wet the wool strips, ensuring that each fiber in the wool strip is uniformly treated thoroughly;
- the roller pressurizes the wool strip to ensure that the wool strip is 130%; then the wool strip with the enzyme liquid is passed to the second treatment tank at a speed of 3.8 m/min.
- the time from the entry of the wool strip into the first tank treatment liquid to the entry into the second tank treatment liquid took 31.5 seconds.
- Second tank padding treatment liquid. Same as the first slot.
- Third tank padding treatment liquid. Same as the first slot.
- Fourth tank padding treatment liquid. Same as the first slot.
- the wool strip is rolled and rolled to clean the reagents, enzymes and degradation products attached to the surface of the wool fiber, and the water temperature is normal temperature and the pH is 7.0.
- Eighth tank secondary washing. Same as the seventh slot.
- the ninth trough high-temperature water washing, playing an enzyme inactivation, to prevent subsequent erosion of wool fibers, temperature 95 ° C, time 15 seconds.
- the tenth trough the tops are padded with a 20g/L wool softener solution to soften the wool fibers to a softening effect and improve the hand.
- the softener solution had a temperature of 40 ° C, a pH of 7.0, and a time of 15 seconds.
- the wool strip is then dehydrated and dried.
- the process speed is 3.8 m / min, and the solution is mixed and treated 6 times.
- the scale stripping effect of wool fiber treated by this process is shown in Fig. 2.
- the wool treated by this process maintained a strength of 83% and an elongation of 72% compared with that before the treatment.
- the 5 ⁇ 5A test result is: -3.82%.
- the chlorine content of the treated wool was examined, and as a result, no residual chlorine component (organic matter) was detected.
- the wool strip is subjected to a chlorine-free shrink-proof treatment by a continuous process of five-fold padding.
- First tank padding treatment liquid.
- the tank is a suction drum tank having a width of 1 meter, a volume of 360 liters and a circumference of one meter, and the suction drum tank has an automatic heating device containing alkaline protease 3g/L and tris(3-carboxypropyl).
- alkaline protease 3g/L and tris(3-carboxypropyl).
- the wool tops are evenly laid flat on the top rollers and fed into the treatment liquid at a speed of 3.8 m/min to completely wet the wool strips, ensuring that each fiber in the wool strip is uniformly treated thoroughly;
- the roller pressurizes the wool strip to ensure that the wool strip is 130%; then the wool strip with the enzyme liquid is passed to the second treatment tank at a speed of 3.8 m/min.
- the time from the entry of the wool strip into the first tank treatment liquid to the entry into the second tank treatment liquid took 31.5 seconds.
- Second tank padding treatment liquid. Same as the first slot.
- Third tank padding treatment liquid. Same as the first slot.
- Fourth tank padding treatment liquid. Same as the first slot.
- the sixth tank washed. a reagent for the adhesion of wool fibers to the surface of the wool fiber by means of a roll of wool, and an enzyme and The degraded product was cleaned, the water temperature was normal temperature, and the pH was 7.0.
- Seventh tank secondary washing. Same as the sixth slot.
- the eighth tank high-temperature water washing, play an enzyme inactivation, to prevent subsequent erosion of wool fiber, temperature 95 ° C, time 15 seconds.
- the ninth trough the tops are padded with a 20g/L wool softener solution to soften the wool fibers to a softening effect and improve the hand.
- the softener solution had a temperature of 40 ° C, a pH of 6.0, and a time of 15 seconds.
- the wool strip is then dehydrated and dried.
- the speed of the process is 3.8 m / min, and the treatment liquid is mixed for 5 times.
- the scale stripping effect of wool fiber treated by this process is shown in Fig. 3.
- the wool treated by this process has a strength of 81% and an elongation of 80% compared with that before the treatment.
- the chlorine content of the treated wool was examined, and as a result, no residual chlorine component (organic matter) was detected.
- the wool strip is subjected to a chlorine-free shrink-proof treatment by a continuous process of five-fold padding.
- the tank is a suction drum tank having a width of 1 meter, a volume of 360 liters and a circumference of one meter.
- the suction drum tank has an automatic heating device, and is mainly filled with alkaline protease 3g/L and three (2-hydroxyethyl).
- alkaline protease 3g/L and three (2-hydroxyethyl.
- the wool tops are evenly laid flat on the top rollers and fed into the treatment liquid at a speed of 4.5 m/min to completely wet the wool strips, ensuring that each fiber in the wool strip is uniformly treated thoroughly;
- the roller pressurizes the wool strip to ensure that the wool strip is 130%; then the wool strip with the enzyme liquid is allowed to enter the second treatment tank at a speed of 4.5 meters per minute.
- the time from the entry of the wool strip into the first tank treatment liquid to the entry into the second tank treatment liquid took 26.7 seconds.
- Second tank padding treatment liquid. Same as the first slot.
- Third tank padding treatment liquid. Same as the first slot.
- Fourth tank padding treatment liquid. Same as the first slot.
- the sixth tank washed.
- the wool strip is rolled and rolled to clean the reagents, enzymes and degradation products attached to the surface of the wool fiber, and the water temperature is normal temperature and the pH is 7.0.
- Seventh tank secondary washing. Same as the sixth slot.
- the eighth tank high-temperature washing, playing an enzyme to prevent the subsequent erosion of wool fiber, temperature 95 °C, time 15 seconds.
- the ninth trough the tops are padded with a 20g/L wool softener solution to soften the wool fibers to a softening effect and improve the hand.
- the softener solution had a temperature of 40 ° C, a pH of 6.0, and a time of 15 seconds.
- the wool strip is then dehydrated and dried.
- the process speed is 4.5 m / min, and the solution is mixed and treated 5 times.
- the scale stripping effect of wool fiber treated by this process is shown in Fig. 4.
- the wool treated by this process maintained a strength of 82% and an elongation of 81% compared with that before the treatment.
- the 5 ⁇ 5A test result is: -3.56%.
- the wool strip is subjected to a chlorine-free shrink-proof treatment by a continuous process of seven-fold padding.
- the tank is a suction drum tank having a width of 1 meter, a volume of 360 liters and a circumference of one meter.
- the suction drum tank has an automatic heating device, and is mainly filled with alkaline protease 2g/L and tris(4-carboxybutyl).
- the wool tops are evenly laid flat on the top rollers and fed into the treatment liquid at a speed of 6 m/min to completely wet the wool strips, ensuring that each fiber in the wool strip is uniformly treated thoroughly;
- the roller pressurizes the wool strip to ensure that the wool strip is 130%; then the wool strip with the enzyme liquid is passed to the second treatment tank at a speed of 6 m/min. It takes 20 seconds from the start of the wool strip to the first tank treatment liquid to the entry into the second tank treatment liquid.
- Second tank padding treatment liquid. Same as the first slot.
- Third tank padding treatment liquid. Same as the first slot.
- Fourth tank padding treatment liquid. Same as the first slot.
- the sixth tank padding treatment liquid. Same as the first slot.
- the eighth tank washed.
- the wool strip is rolled and rolled to clean the reagents, enzymes and degradation products attached to the surface of the wool fiber, and the water temperature is normal temperature and the pH is 7.0.
- the tenth tank high-temperature water washing, play an enzyme inactivation, to prevent subsequent erosion of wool fiber, temperature 95 ° C, time 15 seconds.
- the eleventh trough tops padding 20g / L wool softener solution, softening the wool fiber to achieve softness If you improve your feel.
- the softener solution had a temperature of 40 ° C, a pH of 6.0, and a time of 15 seconds. The wool strip is then dehydrated and dried.
- the process speed is 6 m / min, and the bathing solution is 7 times.
- the scale stripping effect of wool fiber treated by this process is shown in Fig. 5.
- the wool treated by this process maintained a strength of 82% and an elongation of 80% compared with that before the treatment.
- the 5 ⁇ 5A test result is: -3.01%.
- the wool product is subjected to a chlorine-free shrink-proof treatment by a continuous process of quadruple padding.
- the product to be treated is a wool product ( ⁇ ).
- the main components of the treatment liquid are: alkaline protease 1.8g/L, three (4) - Carboxybutyl) phosphine bio-enzyme activator 3.0g / L, anhydrous calcium chloride 0.3g / L (optionally added non-ionic surfactant JFC1g / L) high-efficiency catalytic solution, pH 7.5, control temperature It is 50 °C.
- the flat webs to be treated were sequentially transferred into four groups of Kroy deepim reaction chambers, and the four-fold padding treatment was carried out at a constant speed of 6 m/min for 2 minutes, and the liquid ratio between each group was controlled at 100%, followed by water washing, Inactivated, soft, and dried.
- the wool product not only has good shrink-proof performance, especially the wetting and permeation properties, and the drip diffusion time (according to GB/T21655.1-2008) is improved from ⁇ 10 minutes before treatment to ⁇ 10 seconds.
- the conventional immersion method is used for descaling and shrink-proof treatment as follows:
- the wool strips (70, 20 g) were thoroughly soaked with the soaking treatment solution for 20 minutes or 60 minutes (50 ° C). After the immersion treatment, post treatment (similar to Example 1) was carried out by a conventional method, which included 3 water washings, followed by enzyme inactivation treatment and softening treatment, and finally dehydration and drying.
- the present comparative example adopts a conventional batch type, and is subjected to descaling and shrink-proof treatment by a soaking-steaming method. Methods as below:
- Wool strips (70, 20 g) were fully soaked with a soaking treatment solution (50 ° C, 120% rolling rate), pre-soaked for about 1 minute, and then steamed (50 ° C) in a steaming box for 25 minutes.
- the steaming treatment liquid (the composition is the same as the immersion treatment liquid) is added at the 5th, 10th, 15th and 20th minutes. The soaking-steaming process took a total of 26 minutes.
- Example 2 After the soaking-steaming treatment, it was post-treated by a conventional method (similar to Example 1), which included 3 water washings, followed by enzyme inactivation treatment and softening treatment, and finally dehydration and drying.
- the immersion treatment liquid was similar to the padding treatment liquid solution in Example 1, but did not contain tris(3-hydroxypropyl) phosphine. That is, the formula is as follows: alkaline protease (alkali protease) 3g / L, nonionic surfactant JFC1g / L.
- the sharp corners of the wool surface are substantially completely removed.
- the uniformity is poor, in which the fine wool surface scales are very vague, and the thicker wool scales are thinly cut, indicating that the treatment process has better peeling effect on fine wool scales than coarse wool.
- the fiber strength was 10.34 cN
- the strength retention rate was 83.25%
- the elongation was 32.30%
- the elongation retention rate was 64.77%. This indicates that the wool treated by this process can reach the anti-shrinkage requirement, the breaking strength loss is in an acceptable range, but the elongation loss is relatively large.
- Examples 1-5 of the present invention the entire soaking-steaming process took up to 26 minutes, and the treatment effect was far less than that of Examples 1-5.
- the total time of multiple padding in Examples 1-5 of the present invention is very low ( ⁇ 5 minutes, more preferably ⁇ 3 minutes), and the descaling effect is more uniform, and the shrink-proof property is more excellent.
- the outstanding features of the invention are chlorine-free, rapid continuous processing, to completely replace the chlorination shrinkage prevention method, improve the deficiency of the protease biological treatment process alone, improve the protease biological treatment method, and finally achieve the optimized treatment effect and improve the quality of the whole hair product. the goal of.
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Abstract
Description
Claims (18)
- 一种用于无氯防缩处理的防缩处理剂,其特征在于,所述防缩处理剂包含:(a)任选的溶剂;(b)蛋白酶;和(c)式A所示的有机膦化合物以及任选的无机盐;The anti-shrinkage treatment agent for chlorine-free shrink-proof treatment, characterized in that the shrink-proof treatment agent comprises: (a) an optional solvent; (b) a protease; and (c) an organic compound represented by formula A a phosphine compound and optionally an inorganic salt;P-(X)3 AP-(X) 3 A式中,各X独立地选自下组:取代或未取代的C1-C10烃基,其中所述的取代指具有一个或多个选自下组的取代基:-OH、-COOH(羧基)、C2-C8酯基、-SH、-CN、C1-C3烷基、C1-C3烷氧基;Wherein each X is independently selected from the group consisting of a substituted or unsubstituted C1-C10 hydrocarbon group, wherein said substitution has one or more substituents selected from the group consisting of -OH, -COOH (carboxyl), C2-C8 ester group, -SH, -CN, C1-C3 alkyl group, C1-C3 alkoxy group;并且至少一个X为具有-OH或COOH取代基的取代的C1-C10烃基;And at least one X is a substituted C1-C10 hydrocarbon group having a -OH or COOH substituent;所述的蛋白酶与所述有机膦化合物的重量比为0.2-10:0.5-20;The weight ratio of the protease to the organophosphine compound is 0.2-10:0.5-20;并且所述防缩处理剂中蛋白酶选自下组:中性蛋白酶、碱性蛋白酶、或其组合。And the protease in the anti-shrinkage treatment agent is selected from the group consisting of a neutral protease, an alkaline protease, or a combination thereof.
- 如权利要求1所述的防缩处理剂,其特征在于,当所述防缩处理剂为水溶液或重构为水溶液时,其pH为6.5-12,较佳地为7-11.5,更佳地为7.5-10.5。The anti-shrinkage treatment agent according to claim 1, wherein when the anti-shrinkage treatment agent is an aqueous solution or is reconstituted into an aqueous solution, the pH is 6.5 to 12, preferably 7-11.5, more preferably It is 7.5-10.5.
- 如权利要求1所述的防缩处理剂,其特征在于,所述的有机膦化合物为水溶性脂肪族有机膦化合物。The shrink-proof treatment agent according to claim 1, wherein the organic phosphine compound is a water-soluble aliphatic organophosphine compound.
- 如权利要求1所述的防缩处理剂,其特征在于,所述有机膦化合物具有下式结构:The shrink-proof treatment agent according to claim 1, wherein the organic phosphine compound has the following structure:P-(R1-R2)3 IP-(R 1 -R 2 ) 3 I其中,among them,R1为取代或未取代的C2-C8亚烷基(优选C1-C6亚烷基);和/或R 1 is a substituted or unsubstituted C 2 -C 8 alkylene group (preferably a C 1 -C 6 alkylene group); and/orR2选自下组:-OH、-COOH、或C2-C8酯基、碱金属、或碱土金属。R 2 is selected from the group consisting of -OH, -COOH, or a C2-C8 ester group, an alkali metal, or an alkaline earth metal.
- 如权利要求1所述的防缩处理剂,其特征在于,所述有机膦化合物选自下组:三(3-羟丙基)膦、三(3-羧丙基)膦、三(2-羟乙基)膦、三(4-羧丁基)膦、或其组合。The anti-shrinkage treatment agent according to claim 1, wherein the organophosphine compound is selected from the group consisting of tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, and tris(2- Hydroxyethyl)phosphine, tris(4-carboxybutyl)phosphine, or a combination thereof.
- 一种无氯羊毛条或羊毛制品的防缩处理设备,其特征在于,所述设备包括:A shrink-proof treatment device for a chlorine-free wool strip or a wool product, characterized in that the device comprises:多重浸轧装置,所述多重浸轧装置包括n个独立的、连续排列的浸轧器,所述各浸轧器包括浸泡槽和滚轧辊,其中,所述的浸泡槽用于放置无氯防缩处理的 防缩处理液,使得待处理的羊毛条或羊毛制品浸泡于所述的处理液中;而所述的滚轧辊用于滚轧经浸泡的羊毛条或羊毛制品,并且经上游滚轧辊进行滚轧后羊毛条或羊毛制品,被依次进入下游浸轧器的浸泡槽和滚轧辊,从而重复所述浸泡和滚轧处理,其中n为2-20的正整数;a multiple padding apparatus comprising n independent, continuously arranged padders, each of the paddings comprising a soaking tank and a rolling roll, wherein the soaking tank is used for placing chlorine-free Shrinking The shrink-proof treatment liquid so that the wool strip or wool product to be treated is immersed in the treatment liquid; and the rolling roll is used for rolling the soaked wool strip or wool product, and rolling by the upstream rolling roll a rear wool strip or wool product that is sequentially passed into a soaking tank and a rolling roll of a downstream padder to repeat the soaking and rolling treatment, wherein n is a positive integer of 2-20;水洗装置,用于水洗所述经浸轧的毛条或羊毛制品,形成经水洗的毛条或羊毛制品;a water washing device for washing the padded tops or wool products to form a washed top or wool product;酶灭活装置,用于对所述经水洗的毛条或羊毛制品中的残留的蛋白酶碱性灭活处理,形成经酶灭活的毛条或羊毛制品;An enzyme inactivating device for alkaline inactivation treatment of residual protease in the washed top or wool product to form an enzyme-inactivated top or wool product;任选的柔软处理装置,用于柔软处理所述经酶灭活处理的毛条或羊毛制品,形成经柔软处理的毛条或羊毛制品;和An optional softening device for softening the enzyme-inactivated tops or wool products to form a softened top or wool product;任选的干燥器,用于对上一步骤所得经柔软处理的毛条或羊毛制品进行干燥处理。An optional dryer for drying the softened tops or wool products obtained in the previous step.
- 如权利要求6所述的防缩处理设备,其特征在于,在所述的多重浸轧装置的各浸轧器之间或之后,还设有一个或多个辅助浸轧器,所述的各辅助浸轧器独立地包括辅助浸泡槽和辅助滚轧辊,其中,所述的辅助浸泡槽中放置不含有机膦化合物的蛋白酶处理液,和/或不含蛋白酶的有机膦化合物处理液。The anti-shrinkage treatment apparatus according to claim 6, wherein one or more auxiliary padders are provided between or after each of the padders of said multiple padding apparatus, said auxiliary The padder independently comprises an auxiliary soaking tank and an auxiliary rolling roll, wherein the auxiliary soaking tank is provided with a protease treatment solution containing no organophosphine compound, and/or a protease-free organic phosphine compound treatment liquid.
- 一种无氯羊毛条或羊毛制品的防缩处理方法,其特征在于,包括如下步骤:A method for preventing shrinkage of a chlorine-free wool strip or a wool product, comprising the steps of:(a)提供待处理无氯羊毛条或羊毛制品,以及权利要求1所述的无氯羊毛条或羊毛制品的防缩处理剂;(a) providing a non-chlorinated wool strip or wool product to be treated, and a shrink-proof treatment agent for the chlorine-free wool strip or wool product of claim 1;(b)用所述的防缩处理剂对所述待处理无氯羊毛条或羊毛制品进行n重浸轧处理,从而得到经浸轧的羊毛制品,其中n为2-10的正整数;(b) subjecting the chlorine-free wool strip or wool product to be treated to n-padding treatment with the anti-shrinkage treatment agent, thereby obtaining a padded wool product, wherein n is a positive integer of 2-10;(c)对所述经浸轧的无氯羊毛条或羊毛制品进行水洗处理,得到经水洗的无氯羊毛条或羊毛制品;(c) subjecting the padded chlorine-free wool strip or wool product to a water washing treatment to obtain a water-washed chlorine-free wool strip or wool product;(d)对所述经水洗的无氯羊毛条或羊毛制品进行酶灭活处理,从而得到经防缩处理的无氯羊毛条或羊毛制品。(d) subjecting the water-washed chlorine-free wool strip or wool product to an enzyme inactivation treatment to obtain a shrink-free chlorine-free wool strip or wool product.
- 如权利要求8所述的方法,其特征在于,所述步骤(b)的浸轧处理的总时间T≤15分钟,较佳地≤10分钟,更佳地≤5分钟,最佳地≤3分钟。The method according to claim 8, wherein the total time T of the padding treatment of the step (b) is ≤ 15 minutes, preferably ≤ 10 minutes, more preferably ≤ 5 minutes, most preferably ≤ 3 minute.
- 一种防缩的无氯羊毛产品,其特征在于,所述的羊毛产品中没有有机氯的残留,并且所述的无氯羊毛产品是用权利要求6所述的防缩处理设备进行无氯处理,或用权利要求8所述的方法进行无氯处理的。 A shrink-proof, chlorine-free wool product characterized in that the wool product has no residual organic chlorine, and the chlorine-free wool product is subjected to chlorine-free treatment by the shrink-proof treatment device according to claim 6. Or chlorine-free treatment by the method of claim 8.
- 如权利要求10所述的方法,其特征在于,所述的无氯羊毛产品具有选自下组的4-5个特征:The method of claim 10 wherein said chlorine free wool product has 4-5 characteristics selected from the group consisting of:(a)经所述防缩处理方法处理后,相比于待处理的羊毛产品,经处理的无氯羊毛产品中羊毛表层的鳞片层去除率为80-100%;(a) after treatment by the shrink-proof treatment method, the scale layer removal rate of the wool surface layer in the treated chlorine-free wool product is 80-100% compared to the wool product to be treated;(b)经所述防缩处理方法处理后,相比于待处理的羊毛产品,经处理的无氯羊毛产品的收缩率的绝对值≤5%,最佳地≤3%,其中,测定方法为国际羊毛局TWC.TM31测试方法,(b) after treatment by the shrink-proof treatment method, the absolute value of the shrinkage of the treated chlorine-free wool product is ≤5%, optimally ≤3%, compared to the wool product to be treated, wherein the measuring method For the International Wool Bureau TWC.TM31 test method,(c)经所述防缩处理方法处理后,相比于待处理的羊毛产品,经处理的无氯羊毛产品的强力保持≥80%;(c) after treatment by the shrink-proof treatment method, the strength of the treated chlorine-free wool product is maintained ≥ 80% compared to the wool product to be treated;(d)经所述防缩处理方法处理后,相比于待处理的羊毛产品,经处理的无氯羊毛产品的伸长率保持≥75%;(d) after treatment by the shrink-proof treatment method, the elongation of the treated chlorine-free wool product is maintained ≥75% compared to the wool product to be treated;(e)所述经处理的无氯羊毛产品的滴水扩散时间≤15s。(e) The drip spread time of the treated chlorine-free wool product is ≤ 15 s.
- 一种制品,其特征在于,所述制品包含权利要求10所述的羊毛产品或由权利要求10所述的羊毛产品构成。An article comprising the wool product of claim 10 or the wool product of claim 10.
- 一种权利要求1所述的防缩处理剂的用途,其特征在于,用于对毛条或羊毛制品进行无氯防缩处理。A use of the shrink-proof treatment agent according to claim 1, which is for use in a chlorine-free shrinkage-proof treatment of a top or wool product.
- 一种无氯羊毛条及羊毛制品的防缩处理液,其特征在于,它的主要组成为:蛋白酶、水溶性脂肪族三取代有机膦化合物、无机盐;所述的水溶性脂肪族三取代有机膦结构为:P-(R-S)3,其中R:为含1~6个碳的烃基,S为羟基或羧基及其衍生物;其质量浓度为1~10g/L;无机盐为氯化钙,其浓度为0~2g/L。The anti-shrinkage treatment liquid for chlorine-free wool strips and wool products, characterized in that the main components thereof are: protease, water-soluble aliphatic trisubstituted organic phosphine compound, inorganic salt; said water-soluble aliphatic tri-substituted organic The phosphine structure is: P-(RS) 3 , wherein R: is a hydrocarbon group having 1 to 6 carbons, S is a hydroxyl group or a carboxyl group and a derivative thereof; the mass concentration is 1 to 10 g/L; and the inorganic salt is calcium chloride. , its concentration is 0 ~ 2g / L.
- 如权利要求14所述的防缩处理液,其特征在于,所述的三取代有机膦为:三(3-羟丙基)膦、三(3-羧丙基)膦、三(2-羟乙基)膦、三(4-羧丁基)膦中的至少一种。The anti-shrinkage treatment liquid according to claim 14, wherein the trisubstituted organic phosphine is tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, or tris(2-hydroxyl). At least one of ethylphosphine and tris(4-carboxybutyl)phosphine.
- 一种无氯羊毛条及羊毛制品防缩处理的连续加工工艺,其特征在于,包括以下步骤:The invention relates to a continuous processing technology for anti-shrinkage treatment of chlorine-free wool strips and wool products, which comprises the following steps:1)防缩处理:将羊毛条及羊毛制品排平整通过轧辊匀速输送进入若干装有防缩处理液槽中交替进行浸润与轧压3-10次,工艺条件为:防缩处理液的pH为7~10.5,温度为40~50℃;轧压带液率为60%~150%;工艺输送车速3~15米/分钟,浸润与轧压总时间1~5分钟;1) Anti-shrinkage treatment: the wool strips and wool products are leveled and transported through the rolls at a uniform speed into a plurality of anti-shrinkage treatment tanks alternately infiltrated and rolled 3-10 times. The process conditions are: the pH of the anti-shrinkage treatment liquid is 7~10.5, the temperature is 40~50°C; the rolling liquid rate is 60%~150%; the process conveying speed is 3~15m/min, and the total infiltration and rolling time is 1-5 minutes;2)水洗:将上述处理后的羊毛条通过轧辊作用传输进入1~4个清水槽中进行多次洗涤,以去除残留的生物酶活化剂和酶制剂,防止其继续侵蚀羊毛; 2) Washing: the above treated wool strips are transferred into 1 to 4 clear water tanks by roll action to perform multiple washings to remove residual biological enzyme activators and enzyme preparations to prevent them from continuing to erode the wool;3)蛋白酶的灭活:将第洗涤后的羊毛条均匀快速通过85-95℃热水槽或者为含有双氧水0~1克/升的溶液,将没有完全清洗掉的蛋白酶灭活;3) Inactivation of protease: the washed wool strips are uniformly and quickly passed through a 85-95 ° C hot water tank or a solution containing 0 to 1 g / liter of hydrogen peroxide to inactivate the protease that has not been completely washed;4)柔软处理:将灭活处理后的羊毛条浸泡于常规羊毛平滑剂或有机硅柔软剂的槽中,进行通用的柔软处理,以改善羊毛织物的手感;4) Soft treatment: the inactivated wool strip is soaked in a tank of a conventional wool smoothing agent or a silicone softener, and subjected to a general softening treatment to improve the hand feeling of the wool fabric;5)脱水、烘干;5) dehydration and drying;所述的防缩处理液的主要含有:The anti-shrinkage treatment liquid mainly comprises:三取代有机膦,浓度为1~10g/LTrisubstituted organophosphine at a concentration of 1 to 10 g/L氯化钙,浓度为0.3~2g/LCalcium chloride at a concentration of 0.3 to 2 g/L蛋白酶,浓度为0.5~5g/LProtease at a concentration of 0.5 to 5 g/L其余为水The rest is water所述的三取代有机膦为:三(3-羟丙基)膦、三(3-羧丙基)膦、三(2-羟乙基)膦、三(4-羧丁基)膦中的至少一种。The trisubstituted organic phosphine is: tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, tris(4-carboxybutyl)phosphine At least one.
- 如权利要求16所述的方法,其特征在于,所述的浸泡与挤压或轧压重复进行3-10次;所述的浸泡处理的总时间在1~5分钟之间;工艺输送车速3-8米/分钟。The method according to claim 16, wherein said soaking and pressing or rolling are repeated 3-10 times; the total time of said soaking treatment is between 1 and 5 minutes; and the process conveying speed is 3 -8 m / min.
- 如权利要求16所述的方法,其特征在于,所述羊毛条为56~100支的羊毛或羊绒。 The method of claim 16 wherein said wool strips are from 56 to 100 pieces of wool or cashmere.
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JP2017560863A JP2018506661A (en) | 2015-02-13 | 2016-02-15 | Chlorine-free shrink-proofing processes and equipment used for wool raw materials and products |
US15/551,022 US20180051413A1 (en) | 2015-02-13 | 2016-02-15 | Process and Device for Chlorine-Free Shrinkproof Treatment of Wool Raw Material and Article Thereof |
EP16748752.9A EP3258009A1 (en) | 2015-02-13 | 2016-02-15 | Process and device for chlorine-free shrinkproof treatment of wool raw material and article thereof |
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CN108660773A (en) * | 2018-04-28 | 2018-10-16 | 天津工业大学 | A kind of decrement mellowing method and equipment for matte wool product |
CN109736093A (en) * | 2018-11-22 | 2019-05-10 | 江阴兴吴呢绒科技有限公司 | A kind of felt-proofing finishing method of machine washable wool fabric |
CN110904672A (en) * | 2019-12-19 | 2020-03-24 | 天宇羊毛工业(张家港保税区)有限公司 | Wool top preparation method |
CN113123137A (en) * | 2019-12-31 | 2021-07-16 | 张家港保税区宇联羊毛工业有限公司 | Rapid shrink-proof treatment method for wool tops |
CN112921678A (en) * | 2021-03-24 | 2021-06-08 | 桐乡市恒润皮草有限公司 | Surface treatment method for fur |
CN115613360B (en) * | 2021-07-15 | 2024-07-26 | 上海信诺展创纱业有限公司 | Anti-pilling wool treating agent and method for preparing anti-pilling wool by using same |
CN114232337A (en) * | 2021-12-27 | 2022-03-25 | 罗莱生活科技股份有限公司 | Double-protein acrylic fiber and preparation method thereof |
CN116145421B (en) * | 2022-12-19 | 2023-12-05 | 江苏东智禾新纤维科技有限公司 | Method for preparing anti-pilling wool |
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