CN107217472B - 一种低污染型蚕丝膨化的方法 - Google Patents
一种低污染型蚕丝膨化的方法 Download PDFInfo
- Publication number
- CN107217472B CN107217472B CN201710577854.XA CN201710577854A CN107217472B CN 107217472 B CN107217472 B CN 107217472B CN 201710577854 A CN201710577854 A CN 201710577854A CN 107217472 B CN107217472 B CN 107217472B
- Authority
- CN
- China
- Prior art keywords
- silk
- extruding
- added
- temperature
- low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000011109 contamination Methods 0.000 title claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 230000008961 swelling Effects 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 20
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 13
- 235000019795 sodium metasilicate Nutrition 0.000 claims abstract description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 13
- 239000011592 zinc chloride Substances 0.000 claims abstract description 9
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004202 carbamide Substances 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000009835 boiling Methods 0.000 claims description 15
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 11
- 239000001263 FEMA 3042 Substances 0.000 claims description 11
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 11
- 239000001110 calcium chloride Substances 0.000 claims description 11
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 11
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 11
- 229940033123 tannic acid Drugs 0.000 claims description 11
- 235000015523 tannic acid Nutrition 0.000 claims description 11
- 229920002258 tannic acid Polymers 0.000 claims description 11
- 238000004176 ammonification Methods 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 12
- 235000011121 sodium hydroxide Nutrition 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 238000007906 compression Methods 0.000 description 11
- 230000006835 compression Effects 0.000 description 11
- 235000010855 food raising agent Nutrition 0.000 description 10
- 239000003814 drug Substances 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 235000013904 zinc acetate Nutrition 0.000 description 7
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 7
- 229940007718 zinc hydroxide Drugs 0.000 description 7
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 7
- 108010022355 Fibroins Proteins 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000004110 Zinc silicate Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 235000019352 zinc silicate Nutrition 0.000 description 4
- 208000027418 Wounds and injury Diseases 0.000 description 3
- -1 compound zinc silicate Chemical class 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 208000014674 injury Diseases 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 210000002700 urine Anatomy 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- ZECMMYXDUAUPLX-UHFFFAOYSA-L dizinc chloride hydroxide Chemical compound [Cl-].[Zn+2].[OH-].[Zn+2] ZECMMYXDUAUPLX-UHFFFAOYSA-L 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001007 puffing effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—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 nitrogen or compounds thereof, e.g. with nitrides
- D06M11/59—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 nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
- D06M11/60—Ammonia as a gas or in solution
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/238—Tannins, e.g. gallotannic acids
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Cosmetics (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
本发明公开了一种低污染型蚕丝膨化的方法,其特征在于,包括以下方面:(1)氨化处理,向蒸锅中加入尿素,将蚕丝放置于蒸馏层进行氨化处理;(2)清洗烘干:将蚕丝低温烘干至水分含量为13%‑17%;(3)洗涤膨化,将蚕丝放入滚筒洗涤机中,加入膨化剂进行洗涤膨化处理;(4)平衡溶液,将蚕丝浸入清水中加入氢氧化钠溶液调整溶液至pH6.5‑7;(5)填充膨化,向浸入蚕丝的溶液中分别加入氯化锌、氢氧化钠和硅酸钠,进行填充膨化处理。本发明方法所膨化的蚕丝,其膨化率提高4.78%,膨化效果好,收缩率低,单位面积质量增加0.411g,具有良好的膨松性和下垂性。
Description
技术领域
本发明属于蚕丝加工技术领域,具体涉及一种低污染型蚕丝膨化的方法。
背景技术
蚕丝是由丝胶和丝素组成,其中丝胶包裹在丝素外部,占到总质量20%-25%,对丝素起到粘连和保护作用,而其中丝素就是蚕丝加工的主要成分,其性质功能直接决定蚕丝的优劣,丝素微观下成并性排列纤维状,并且蚕丝纤维存在微孔,会对水分子等小分子物质进行吸附。丝素蚕丝的膨化性,直接影响到蚕丝加工制品的柔软性和舒适性;膨松丝是由低温药煮、低张力缫制或者其他化学方法处理而得的新型丝,其丝质比普通真丝更加膨松、柔软,其纺织产品既柔软又挺括,既膨松、丰满又富有骨和回弹性等风格,所织布料轻质柔软、挺拔性能好、不易褶皱,具有优良的加工和穿着性。蚕丝的膨化处理目前主要采取加热蒸煮方法和药剂浸泡方法,其中加热蒸煮方法,是将蚕丝进行加热处理通过蚕丝受热膨胀产生蚕丝膨化,但是当温度下降后蚕丝会收缩,膨化效果下降;而使用药剂浸泡方法,通过向加热溶剂中加入膨化剂、表面活性剂等成分,蚕丝内部结构受力情况发生变化,结构出现疏松,并且通过其它成分的添加,使蚕丝膨化后空隙处填充添加成分 ,减少了蚕丝的收缩性;但是,所使用药剂中包括膨化剂、稳定剂、乳化剂、活性剂等大量的化合物成分,造成药剂溶液成分复杂,而且多为有机化合物,难以降解处理、污染程度高。
发明内容
本发明针对现有的问题:蚕丝膨化性能,经膨化处理后蚕丝膨松柔软,织布料轻质柔软、挺拔性能好、不易褶皱,具有优良的加工和穿着性,可以较大程度上提高蚕丝的加工性能。加热蒸煮方法,是将蚕丝进行加热处理通过蚕丝受热膨胀产生蚕丝膨化,但是当温度下降后蚕丝会收缩,膨化效果下降;药剂浸泡方法,通过向加热溶剂中加入膨化剂、表面活性剂等成分,蚕丝内部结构受力情况发生变化,结构出现疏松,并且通过其它成分的添加,使蚕丝膨化后空隙处填充添加成分 ,减少了蚕丝的收缩性;但是,所使用药剂中包括膨化剂、稳定剂、乳化剂、活性剂等大量的化合物成分,造成药剂溶液成分复杂,而且多为有机化合物,难以降解处理、污染程度高。为解决上述问题,本发明提供了一种低污染型蚕丝膨化的方法。
本发明是通过以下技术方案实现的:
一种低污染型蚕丝膨化的方法,包括以下步骤:
(1)氨化处理:将脱胶蚕丝放置于蒸锅蒸馏层,向蒸锅水中加入水质量13%-15%的尿素,蒸煮中产生氨气,氨气在水蒸气中溶解产生铵根离子和氢氧根离子,氢氧根离子可破坏蚕丝内部作用力的平衡,减弱蚕丝内部相互作用力,增加膨松效果,关闭锅盖,先将蒸锅加热至66-69℃蒸煮20-24min,再将温度提升至93-97℃蒸煮30-35min,冷却降温速度为5℃/3min,制得氨化蚕丝;
(2)清洗烘干:将氨化蚕丝低温烘干,至蚕丝中水分含量为13%-17%;
(3)洗涤膨化:将烘干后蚕丝放入滚筒洗涤机中,滚筒洗涤机对蚕丝产生的轻揉搓力,可使蚕丝、膨松剂和滚筒在旋转中相互作用和融合,促进了膨松剂对蚕丝的渗透作用,向滚筒洗涤机中加入蚕丝质量17%-20%的膨化剂,其中单宁酸可对蚕丝进行膨化作用,氯化钙作为填充物质填充至蚕丝纤维内部间隙,提高膨松状态,并且提高蚕丝的干燥性能,而醋酸锌和醋酸可起到调节酸碱平衡和填充的作用,进行洗涤膨化处理,洗涤温度为44-47℃,洗涤转速35-38转/min,时间40-50min,其中温度上升速度为4℃/5min,转速提高速度为5转/3min,可防止快速提高温度和转速对蚕丝产生的伤害,制得洗涤膨化蚕丝;
(4)平衡溶液:将洗涤膨化蚕丝浸入清水中加入氢氧化钠溶液,调整溶液至pH6.5-7,降低溶液中酸性,为后续处理提供中性溶液环境;
(5)填充膨化:将平衡调节后蚕丝浸入23-27℃反应釜水中,向反应釜中加入其水质量4%-6%的氯化锌,搅拌反应46-52min,氯化锌加热后进入蚕丝的纤维间隙中,再向反应釜中加入2%-3%的氢氧化钠溶液,反应釜温度提升至65-69℃,保持25-30min,与氯化锌反应产生氢氧化锌沉淀,在蚕丝纤维间隙中形成填充物,提高蚕丝的膨松性,减少蚕丝收缩,然后向反应釜中加入1.5%-2%的硅酸钠,反应釜温度调整至52-55℃,保持32-36min,硅酸钠水解后会产生硅酸,硅酸与氢氧化锌发生反应形成更为稳定的化合物硅酸锌,从而达到更好的填充蚕丝纤维的作用,保持良好的膨松状态,并且提高了蚕丝重量,具有更好防皱性能;将蚕丝经清水洗涤、烘干后制得膨化蚕丝。
步骤(2)所述的低温烘干,其温度为51-54℃,时间为34-38min。
步骤(3)所述的膨化剂,其配制方法为:
按照质量计份称取水34-39份、单宁酸14-18份、氯化钙7-10份、醋酸锌6-8份、醋酸6-8份,将水加热至47-52℃加入单宁酸和氯化钙,搅拌混合3-5min,然后将温度降至35-38℃加入醋酸锌和醋酸,搅拌混合后制得膨化剂。
步骤(4)所述的氢氧化钠溶液,其质量浓度为1%。
步骤(5)所述的氢氧化钠溶液,其质量浓度为1%;所述的硅酸钠,其质量浓度为4%-5%。
本发明相比现有技术具有以下优点:氨化处理,通过对尿素蒸煮使其分解产生氨气,氨气在水蒸气中溶解产生铵根离子和氢氧根离子,其中产生的氢氧根离子通过蒸汽渗透作用与蚕丝中的氢键发生作用,而蚕丝通过范德华力和氢键等作用力保持其紧密性,降低了蚕丝内部的作用力,对蚕丝起到初步膨化作用,降低蚕丝内部相互作用力,提高膨化程度。洗涤膨化,将蚕丝放入滚筒洗涤机中,滚筒洗涤机对蚕丝产生的轻揉搓力,可使蚕丝、膨松剂和滚筒在旋转中相互作用和融合,促进了膨松剂对蚕丝的渗透作用;其中膨松剂中单宁酸对蚕丝具有膨化作用,氯化钙可对膨松后蚕丝间隙进行部分填充,而醋酸锌和醋酸作为缓冲剂调节酸碱平衡,并对蚕丝起到膨化和填充作用。填充膨化,蚕丝纤维在微观下具有一定间隙,可对环境中小分子物质进行吸附,而经过初步膨化和洗涤膨化后蚕丝,其蚕丝纤维内部间隙增大,通过向水中加入氯化锌,在加热作用下进入蚕丝纤维内部,并与加入的氢氧化钠反应形成氢氧化锌沉淀,在蚕丝纤维内部形成填充物,而加入的硅酸钠在水中水解中产生硅酸与氢氧化锌进一步反应,产生性质更为稳定的硅酸锌,提高了蚕丝中填充物的稳定性,并且通过填充物的填充作用降低了蚕丝的收缩,能够长时间保持膨松状态,并且增加了蚕丝的增重了,可提高蚕丝及蚕丝制品的下垂状态。本发明方法中所用化学试剂均为无机试剂,其成分简单、污染性小,可以对使用后溶液进行有效的处理,将对环境的污染降至最低限度。
具体实施方式
实施例1:
一种低污染型蚕丝膨化的方法,包括以下步骤:
(1)氨化处理:将脱胶蚕丝放置于蒸锅蒸馏层,向蒸锅水中加入水质量13.5%的尿素,蒸煮中产生氨气,氨气在水蒸气中溶解产生铵根离子和氢氧根离子,氢氧根离子可破坏蚕丝内部作用的力的平衡,减弱蚕丝相互作用力,关闭锅盖,先将蒸锅加热至67℃蒸煮21min,再将温度提升至94℃蒸煮32min,冷却降温速度为5℃/3min,制得氨化蚕丝;
(2)清洗烘干:将氨化蚕丝低温烘干,至蚕丝中水分含量为14%;
(3)洗涤膨化:将烘干后蚕丝放入滚筒洗涤机中,滚筒洗涤机对蚕丝产生的轻揉搓力,可使蚕丝、膨松剂和滚筒在旋转中相互作用和融合,促进了膨松剂对蚕丝的渗透作用,向滚筒洗涤机中加入蚕丝质量18%的膨化剂,其中单宁酸可对蚕丝进行膨化作用,氯化钙作为填充物质填充至蚕丝纤维内部间隙,提高膨松状态,并且提高蚕丝的干燥性能,进行洗涤膨化处理,洗涤温度为45℃,洗涤转速36转/min,时间42min,其中温度上升速度为4℃/5min,转速提高速度为5转/3min,可防止快速提高温度和转速对蚕丝产生的伤害,制得洗涤膨化蚕丝;
(4)平衡溶液:将洗涤膨化蚕丝浸入清水中加入氢氧化钠溶液,调整溶液至pH6.5-7,降低溶液中酸性,为后续处理提供中性溶液环境;
(5)填充膨化:将平衡调节后蚕丝浸入24℃反应釜水中,向反应釜中加入其水质量4.5%的氯化锌,搅拌反应48min,进入蚕丝的纤维间隙中,再向反应釜中加入2.2%的氢氧化钠溶液,反应釜温度提升至66℃,保持27min,与氯化锌反应产生氢氧化锌沉淀,在蚕丝纤维间隙中形成填充物,提高蚕丝的膨松状态,减少收缩,然后向反应釜中加入1.7%的硅酸钠,反应釜温度调整至53℃,保持34min,硅酸钠水解后会产生硅酸,硅酸与氢氧化锌发生反应形成更为稳定的化合物硅酸锌,从而达到更好的填充蚕丝纤维的作用,保持良好的膨松状态,并且提高了蚕丝重量,具有更好防皱性能;将蚕丝经清水洗涤、烘干后制得膨化蚕丝。
步骤(2)所述的低温烘干,其温度为52℃,时间为35min。
步骤(3)所述的膨化剂,其配制方法为:
按照质量计份称取水36份、单宁酸15份、氯化钙8份、醋酸锌6.5份、醋酸6.5份,将水加热至49℃加入单宁酸和氯化钙,搅拌混合3.5min,然后将温度降至36℃加入醋酸锌和醋酸,搅拌混合后制得膨化剂。
步骤(4)所述的氢氧化钠溶液,其质量浓度为1%。
步骤(5)所述的氢氧化钠溶液,其质量浓度为1%;所述的硅酸钠,其质量浓度为4.2%。
实施例2:
一种低污染型蚕丝膨化的方法,包括以下步骤:
(1)氨化处理:将脱胶蚕丝放置于蒸锅蒸馏层,向蒸锅水中加入水质量14.5%的尿素,蒸煮中产生氨气,氨气在水蒸气中溶解产生铵根离子和氢氧根离子,氢氧根离子可破坏蚕丝内部作用的力的平衡,减弱蚕丝相互作用力,关闭锅盖,先将蒸锅加热至68℃蒸煮23min,再将温度提升至96℃蒸煮34min,冷却降温速度为5℃/3min,制得氨化蚕丝;
(2)清洗烘干:将氨化蚕丝低温烘干,至蚕丝中水分含量为16%;
(3)洗涤膨化:将烘干后蚕丝放入滚筒洗涤机中,滚筒洗涤机对蚕丝产生的轻揉搓力,可使蚕丝、膨松剂和滚筒在旋转中相互作用和融合,促进了膨松剂对蚕丝的渗透作用,向滚筒洗涤机中加入蚕丝质量19%的膨化剂,其中单宁酸可对蚕丝进行膨化作用,氯化钙作为填充物质填充至蚕丝纤维内部间隙,提高膨松状态,并且提高蚕丝的干燥性能,进行洗涤膨化处理,洗涤温度为46℃,洗涤转速37转/min,时间48min,其中温度上升速度为4℃/5min,转速提高速度为5转/3min,可防止快速提高温度和转速对蚕丝产生的伤害,制得洗涤膨化蚕丝;
(4)平衡溶液:将洗涤膨化蚕丝浸入清水中加入氢氧化钠溶液,调整溶液至pH6.5-7,降低溶液中酸性,为后续处理提供中性溶液环境;
(5)填充膨化:将平衡调节后蚕丝浸入26℃反应釜水中,向反应釜中加入其水质量5.4%的氯化锌,搅拌反应51min,进入蚕丝的纤维间隙中,再向反应釜中加入2.8%的氢氧化钠溶液,反应釜温度提升至68℃,保持29min,与氯化锌反应产生氢氧化锌沉淀,在蚕丝纤维间隙中形成填充物,提高蚕丝的膨松状态,减少收缩,然后向反应釜中加入1.8%的硅酸钠,反应釜温度调整至54℃,保持35min,硅酸钠水解后会产生硅酸,硅酸与氢氧化锌发生反应形成更为稳定的化合物硅酸锌,从而达到更好的填充蚕丝纤维的作用,保持良好的膨松状态,并且提高了蚕丝重量,具有更好防皱性能;将蚕丝经清水洗涤、烘干后制得膨化蚕丝。
步骤(2)所述的低温烘干,其温度为53℃,时间为37min。
步骤(3)所述的膨化剂,其配制方法为:
按照质量计份称取水37份、单宁酸16份、氯化钙9份、醋酸锌7.2份、醋酸7.2份,将水加热至51℃加入单宁酸和氯化钙,搅拌混合4min,然后将温度降至37℃加入醋酸锌和醋酸,搅拌混合后制得膨化剂。
步骤(4)所述的氢氧化钠溶液,其质量浓度为1%。
步骤(5)所述的氢氧化钠溶液,其质量浓度为1%;所述的硅酸钠,其质量浓度为4.8%。
对比1:
本对比1与实施例1比较,未进行步骤(1)氨化处理,其他步骤与实施例1相同。
对比2:
本对比2与实施例2比较,未进行步骤(3)洗涤膨化,其他步骤与实施例2相同。
对比3:
本对比3与实施例2比较,未进行步骤(3)中膨松剂的使用,其他步骤与实施例2相同。
对比4:
本对比4与实施例1比较,未进行步骤(5)填充膨化,其他步骤与实施例1相同。
对照组:
对照组对蚕丝使用药剂浸泡膨化方法,未使用氨化处理、洗涤膨化和填充膨化。
对实施例1、实施例2、对比1、对比2、对比3、对比4及对照组实验方案,统计蚕丝的压缩率、压缩恢复率、膨化率及单位面积质量。
压缩恢复率:为膨化后蚕丝制成蚕丝被,进行下压后20min内恢复原状的比例。
膨化率:膨化率=(膨化后纤维直径-膨化前纤维直径)/膨化前纤维直径。
单位面积质量:使用相同工艺将蚕丝纺织成相同布料,其每平方厘米面积的质量。
实验数据:
项目 | 压缩率% | 压缩恢复率% | 膨化率% | 单位面积质量g |
实施例1 | 17.35% | 84.73% | 19.45% | 3.2745 |
实施例2 | 17.14% | 84.29% | 19.16% | 3.3612 |
对比1 | 16.22% | 81.86% | 18.37% | 3.1704 |
对比2 | 15.67% | 81.03% | 17.84% | 3.2397 |
对比3 | 16.29% | 82.75% | 18.59% | 3.3036 |
对比4 | 14.81% | 79.28% | 17.30% | 3.0667 |
对照组 | 11.98% | 72.68% | 14.67% | 2.8635 |
综合结果:本发明方法所膨化的蚕丝,其膨化率提高4.78%,膨化效果好,收缩率低,单位面积质量增加0.411g,具有良好的膨松性和下垂性。通过使用氨化处理方法,压缩率提高1.13%,压缩恢复率提高2.87%,膨化率提高1.08%,单位面积质量提高0.1041g;而使用洗涤膨化和膨松剂,压缩率提高1.47%、0.85%,压缩恢复率提高3.26%、1.54%,膨化率提高1.32%、0.57%,单位面积质量提高0.1215g、0.0576g;使用填充膨化方法,压缩率提高2.54%,压缩恢复率提高5.45%,膨化率提高2.15%,单位面积质量提高0.2078g。
Claims (4)
1.一种低污染型蚕丝膨化的方法,其特征在于,包括以下步骤:
(1)氨化处理:将脱胶蚕丝放置于蒸锅蒸馏层,向蒸锅水中加入水质量13%-15%的尿素,关闭锅盖,先将蒸锅加热至66-69℃蒸煮20-24min,再将温度提升至93-97℃蒸煮30-35min,冷却降温速度为5℃/3min,制得氨化蚕丝;
(2)清洗烘干:将氨化蚕丝低温烘干,至蚕丝中水分含量为13%-17%;
(3)洗涤膨化:将烘干后蚕丝放入滚筒洗涤机中,向滚筒洗涤机中加入蚕丝质量17%-20%的膨化剂,进行洗涤膨化处理,洗涤温度为44-47℃,洗涤转速35-38转/min,时间40-50min,其中温度上升速度为4℃/5min,转速提高速度为5转/3min,制得洗涤膨化蚕丝;
(4)平衡溶液:将洗涤膨化蚕丝浸入清水中加入氢氧化钠溶液,调整溶液至pH6.5-7;
(5)填充膨化:将平衡调节后蚕丝浸入23-27℃反应釜水中,向反应釜中加入其水质量4%-6%的氯化锌,搅拌反应46-52min,再向反应釜中加入2%-3%的氢氧化钠溶液,反应釜温度提升至65-69℃,保持25-30min,然后向反应釜中加入1.5%-2%的硅酸钠,反应釜温度调整至52-55℃,保持32-36min;将蚕丝经清水洗涤、烘干后制得膨化蚕丝;
步骤(3)所述的膨化剂,其配制方法为:
按照质量计份称取水34-39份、单宁酸14-18份、氯化钙7-10份、醋酸锌6-8份、醋酸6-8份,将水加热至47-52℃加入单宁酸和氯化钙,搅拌混合3-5min,然后将温度降至35-38℃加入醋酸锌和醋酸,搅拌混合后制得膨化剂。
2.如权利要求1所述低污染型蚕丝膨化的方法,其特征在于,步骤(2)所述的低温烘干,其温度为51-54℃,时间为34-38min。
3.如权利要求1所述低污染型蚕丝膨化的方法,其特征在于,步骤(4)所述的氢氧化钠溶液,其质量浓度为1%。
4.如权利要求1所述低污染型蚕丝膨化的方法,其特征在于,步骤(5)所述的氢氧化钠溶液,其质量浓度为1%;所述的硅酸钠,其质量浓度为4%-5%。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710577854.XA CN107217472B (zh) | 2017-07-15 | 2017-07-15 | 一种低污染型蚕丝膨化的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710577854.XA CN107217472B (zh) | 2017-07-15 | 2017-07-15 | 一种低污染型蚕丝膨化的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107217472A CN107217472A (zh) | 2017-09-29 |
CN107217472B true CN107217472B (zh) | 2019-11-08 |
Family
ID=59952334
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710577854.XA Expired - Fee Related CN107217472B (zh) | 2017-07-15 | 2017-07-15 | 一种低污染型蚕丝膨化的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107217472B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112210260A (zh) * | 2020-10-14 | 2021-01-12 | 东莞狐马商贸有限公司 | 一种自组装丝素纳米纤维改性的聚合物涂料的制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1435432A (zh) * | 2002-12-11 | 2003-08-13 | 内蒙古鄂尔多斯羊绒集团有限责任公司 | 一种角蛋白溶液和固体制备技术 |
CN103696298A (zh) * | 2013-12-23 | 2014-04-02 | 嘉兴学院 | 一种低损伤羊毛织物砂洗整理工艺 |
CN106049033A (zh) * | 2016-06-29 | 2016-10-26 | 广西南宁马山东龙蚕业有限责任公司 | 一种蚕丝膨化的方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1195233A (en) * | 1966-07-26 | 1970-06-17 | Johnson & Johnson | Nonwoven fibrous product and method of making the same. |
CN105484028A (zh) * | 2015-12-18 | 2016-04-13 | 张莘蔓 | 一种蚕丝膨化的方法 |
-
2017
- 2017-07-15 CN CN201710577854.XA patent/CN107217472B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1435432A (zh) * | 2002-12-11 | 2003-08-13 | 内蒙古鄂尔多斯羊绒集团有限责任公司 | 一种角蛋白溶液和固体制备技术 |
CN103696298A (zh) * | 2013-12-23 | 2014-04-02 | 嘉兴学院 | 一种低损伤羊毛织物砂洗整理工艺 |
CN106049033A (zh) * | 2016-06-29 | 2016-10-26 | 广西南宁马山东龙蚕业有限责任公司 | 一种蚕丝膨化的方法 |
Also Published As
Publication number | Publication date |
---|---|
CN107217472A (zh) | 2017-09-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2019101766A4 (en) | Skincare and antibacterial microcapsule finishing agent, and preparation method therefor and application thereof | |
CN105200802B (zh) | 一种具有保健功能的香氛轻薄羊毛面料的制备方法 | |
CN104988742B (zh) | 一种棉质衬衫的凉感免烫处理方法 | |
CN112921647B (zh) | 一种对涤纶的抗熔滴整理方法 | |
CN106436309A (zh) | 一种阻燃抗菌棉麻混纺织物面料的生产方法 | |
CN105568665B (zh) | 一种拒污防毡缩羊毛面料的生产方法 | |
TW201504348A (zh) | 獲得防水及/或防水溶性污垢的織物的方法及組成物 | |
CN104762821A (zh) | 一种蚕丝织物的免烫整理方法 | |
CN108998970B (zh) | 一种棉织物用无甲醛抗皱整理剂的制备方法及应用 | |
CN107217472B (zh) | 一种低污染型蚕丝膨化的方法 | |
CN105544205B (zh) | 一种透气保暖空气层面料 | |
CN107044051A (zh) | 一种羊毛面料的芳香防蛀整理工艺 | |
CN107815862A (zh) | 多羧酸预聚体无甲醛抗皱防缩整理剂及对织物的整理方法 | |
CN105506954B (zh) | 一种羊毛激光冲孔镂空面料的制备方法 | |
CN113863012A (zh) | 一种聚酯纤维与棉纤维混纺面料及其制备工艺 | |
CN105506951B (zh) | 一种透气型轻薄双面镂空面料 | |
CN105506949B (zh) | 一种单面防毡缩羊毛面料的制备方法 | |
CN105696334A (zh) | 一种针织物的抗起球后整理工艺 | |
CN112962313B (zh) | 一种与水性聚氨酯复配的棉织物免烫整理液、制备方法及其应用 | |
CN101575805B (zh) | 一种纳米真丝抗皱针织服装的生产工艺 | |
CN114575150A (zh) | 一种芳香耐久型帽饰用纯棉布及其制备方法 | |
CN105860801A (zh) | 一种含超细羽绒纤维-有机硅微球的水性聚氨酯涂层剂 | |
CN105239383A (zh) | 一种基于液体冷冻的婴幼儿用新型改性棉纤维及其制备工艺 | |
CN104404755A (zh) | 一种抗皱的真丝面料的制备方法 | |
CN112647283B (zh) | 具有高散湿性的改性蚕丝纤维及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191108 |
|
CF01 | Termination of patent right due to non-payment of annual fee |