KR102097119B1 - Manufacturing method of polyurethane resin for textile processing agent having high durability, polyurethane resin for textile processing agent using the same, polyurethane base textile processing agent using the same and textile processing method of using the polyurethane base textile processing agent - Google Patents
Manufacturing method of polyurethane resin for textile processing agent having high durability, polyurethane resin for textile processing agent using the same, polyurethane base textile processing agent using the same and textile processing method of using the polyurethane base textile processing agent Download PDFInfo
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- KR102097119B1 KR102097119B1 KR1020180121861A KR20180121861A KR102097119B1 KR 102097119 B1 KR102097119 B1 KR 102097119B1 KR 1020180121861 A KR1020180121861 A KR 1020180121861A KR 20180121861 A KR20180121861 A KR 20180121861A KR 102097119 B1 KR102097119 B1 KR 102097119B1
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 73
- 238000012545 processing Methods 0.000 title claims abstract description 69
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 29
- 239000004814 polyurethane Substances 0.000 title claims abstract description 29
- 239000004753 textile Substances 0.000 title claims abstract description 29
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000003672 processing method Methods 0.000 title claims description 8
- 239000000835 fiber Substances 0.000 claims description 56
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000004744 fabric Substances 0.000 claims description 17
- 229920005862 polyol Polymers 0.000 claims description 16
- 150000003077 polyols Chemical class 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 239000012948 isocyanate Substances 0.000 claims description 14
- 150000002513 isocyanates Chemical class 0.000 claims description 14
- 230000003472 neutralizing effect Effects 0.000 claims description 13
- 239000004970 Chain extender Substances 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001610 polycaprolactone Polymers 0.000 claims description 11
- 239000004632 polycaprolactone Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 229920001451 polypropylene glycol Polymers 0.000 claims description 11
- 239000002981 blocking agent Substances 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 125000003010 ionic group Chemical group 0.000 claims description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 6
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 claims description 4
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 4
- XKQMKMVTDKYWOX-UHFFFAOYSA-N 1-[2-hydroxypropyl(methyl)amino]propan-2-ol Chemical compound CC(O)CN(C)CC(C)O XKQMKMVTDKYWOX-UHFFFAOYSA-N 0.000 claims description 4
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- WHIVNJATOVLWBW-SNAWJCMRSA-N methylethyl ketone oxime Chemical group CC\C(C)=N\O WHIVNJATOVLWBW-SNAWJCMRSA-N 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims description 2
- JRQLZCFSWYQHPI-UHFFFAOYSA-N 4,5-dichloro-2-cyclohexyl-1,2-thiazol-3-one Chemical compound O=C1C(Cl)=C(Cl)SN1C1CCCCC1 JRQLZCFSWYQHPI-UHFFFAOYSA-N 0.000 claims description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 2
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 2
- 229940093858 ethyl acetoacetate Drugs 0.000 claims description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 25
- 238000005406 washing Methods 0.000 abstract description 12
- 238000001035 drying Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 11
- 230000008859 change Effects 0.000 description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 8
- 230000037303 wrinkles Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 230000002265 prevention Effects 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 230000001153 anti-wrinkle effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229940015043 glyoxal Drugs 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000010409 ironing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- -1 polysiloxane Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XHJGXOOOMKCJPP-UHFFFAOYSA-N 2-[tert-butyl(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(C(C)(C)C)CCO XHJGXOOOMKCJPP-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229940117969 neopentyl glycol Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- LGJMYGMNWHYGCB-UHFFFAOYSA-N 4,5-dihydroxy-1,3-dimethylimidazolidin-2-one Chemical compound CN1C(O)C(O)N(C)C1=O LGJMYGMNWHYGCB-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 210000003899 penis Anatomy 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 230000037330 wrinkle prevention Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
본 발명은 포르말린 등의 유해 성분을 배제한 비포르말린 타입이면서도 세탁 및 세탁 후 건조 시에 치수변화 방지 성능 및 형태 유지력 등의 내구성을 향상시킬 수 있도록 하는, 섬유 가공제용 폴리우레탄 수지의 제조방법, 이 방법에 의해 제조된 섬유 가공제용 폴리우레탄 수지, 이를 이용하여 제조되는 폴리우레탄계 섬유 가공제 및 이 폴리우레탄계 섬유 가공제를 이용한 섬유 가공방법에 관한 것이다.The present invention is a non-formalin type excluding harmful components such as formalin, but also a method for manufacturing a polyurethane resin for textile processing agents to improve durability such as dimensional change prevention performance and shape retention when washing and drying after washing, this method It relates to a polyurethane resin for a fiber processing agent produced by, a polyurethane-based fiber processing agent produced using the same and a fiber processing method using the polyurethane-based fiber processing agent.
일반적으로 셀룰로오스계 섬유는 쾌적성이 좋고, 내구성이 우수하며, 저렴한 가격 및 좋은 염색성 등의 장점을 갖고 있어서, 흔히 의류의 소재로 많이 사용되고 있으나, 셀룰로오스계 섬유는 세탁후 또는 착용중에 구김이 잘 생기고 또한, 그 회복성이 낮다는 큰 결점도 함께 지니고 있다.In general, cellulose fibers have good comfort, excellent durability, low price, and good dyeing properties, and are often used as a material for clothing, but cellulose fibers tend to wrinkle well after washing or wearing. In addition, it also has a large drawback of low recovery.
이러한 의류에 발생되는 구김의 발생에 영향을 주는 인자로서는, 섬유의 종류, 섬유의 분자형태 및 배열방법, 꼬임수 또는 번수, 직물의 밀도, 두께 등과 같은 구조적인 변수와, 온도, 습도, 외력, 시간 등과 같은 외부 환경 등이 있으며, 이러한 요인에 의해서, 화학적 결합의 재배열이나 구조적 특성이 변화됨으로써 구김이 발생하게 되는 것이다.Structural variables such as the type of fiber, the molecular shape and arrangement method of the fiber, the number or number of twists, the density and thickness of the fabric, and the temperature, humidity, and external force as factors affecting the generation of wrinkles generated in such clothing, There are external environments such as time, etc., and due to these factors, the rearrangement of chemical bonds or structural properties change, resulting in wrinkles.
상기와 같은 요인으로 인해서 발생된 구김을 개선시키는 방법으로는 다음과 같은 방법이 종래에 사용되고 있다. 셀룰로오스계 직물에 산처리, 알칼리처리, 방축 가공 등과 같은 수지가공, 에이징(Aging), 아닐링(Annealing) 등과 같은 화학적 처리방법과 직물의 구조적 변수를 변경하거나 혼방을 통한 물리적 구조변경 방법이 그것이다.The following methods are conventionally used as a method for improving wrinkles caused by the above factors. These are chemical processing methods such as resin processing such as acid treatment, alkali treatment, and pre-shrinkage processing on cellulose-based fabrics, chemical treatment methods such as aging, annealing, etc., and changes in the structural parameters of fabrics or physical structure changes through blending. .
대부분 셀룰로오스계 섬유의 구김은 수축에 의해 발생되는 경향이 크고, 산이나 알칼리로 처리하는 방법은 직물의 손상이 크기 때문에, 공업적으로는 통상 주름방지 가공수지를 사용한 화학적처리 방법과 폴리에스테르와 같이 구김성이 적은 섬유와의 혼방을 이용하는 물리적 방법이 많이 이용되고 있다.Most wrinkles of cellulose-based fibers tend to be caused by shrinkage, and the method of treating with acid or alkali is largely damaging to the fabric. A number of physical methods using blends with fibers with less wrinkles have been used.
현재까지는, 셀룰로오스계 섬유와 같은 구김이 많이 발생하는 의류의 주름방지 가공으로는 대부분이 기성복 제조과정중에서 공업적 규모로 행해지고 있으나, 이는 저가의 포르말린계 수지나 가스 등의 처리에 의한 것이므로 피부에 유해하다는 단점을 가지고 있다.Until now, most of wrinkle-free processing of wrinkled clothing such as cellulose fibers has been performed on an industrial scale during the manufacture of ready-made clothing, but this is due to treatment with low-priced formalin-based resins or gases, and is therefore harmful to the skin. It has the disadvantage of being.
또한, 직물은 직물의 처리과정에서 주름방지 가공을 하는 것이 일반적인 것이어서 봉제하고자 하는 직물은 주름방지 가공처리가 되어 있는 반면에 의류의 본제를 위하여 사용되는 봉제사는 방축가공이 되지 않은 상태에서 사용이 되므로 제조된 제품은 세탁후 봉제선 부분에 물결모양의 퍼커링이 발생하고 또한 반복 세탁으로 인하여 주름방지 효과가 현저히 감소한다는 단점을 갖고 있다.In addition, since the fabric is generally wrinkle-prevented during the processing of the fabric, the fabric to be sewn is treated with anti-wrinkle, whereas the sewing thread used for the agent of clothing is used without pre-shrinkage. The manufactured product has a disadvantage that wavy puckering occurs on the seam after washing, and the anti-wrinkle effect is significantly reduced due to repeated washing.
상기와 같은 문제점을 해결하기 위하여 공업적으로는 글리옥살계 수지를 기본으로 하는 방축수지로 불리우는 메티롤화된 요소계수지를 사용하여 처리하고 다림질을 하는 방법이 사용되기도 하였으나, 이 경우에 있어서는 다림질 도중에 제품으로 부터 열분해에 의한 인체에 해로운 포름알데히드가 작업환경을 오염시키는 문제가 있었다.In order to solve the above problems, a method of treating and ironing using a methirolated urea resin called a preshrunk resin based on glyoxal resin was also used, but in this case, during ironing. There was a problem that formaldehyde, which is harmful to the human body by thermal decomposition from the product, pollutes the working environment.
상기와 같은 문제점을 보완하기 위한 방법으로 인체에 무해한 비포르말린계 주름방지 가공수지와 염화마그네슘으로 구성된 포르마린을 함유하지 않는 유해성이 낮은 약품으로 된 가공제를 직접 스프레이하고, 이를 다림질을 통해서 경화시킴으로서 의류에 형상가공을 시킬 수 있는 방법이 제안된 바 있다.As a method to compensate for the above problems, clothing is made by directly spraying a processing agent made of a non-malignant anti-wrinkle processing resin that is harmless to the human body and a low-toxic chemical agent composed of magnesium chloride, and curing it through ironing. There has been proposed a method that can be used for shape processing.
그러나, 비포르말린계 글리옥살수지와 염화마그네슘염을 촉매로 사용한 가정용 섬유 가공방법에서 사용되는 비포르말린계 글리옥살수지는 반응기가 2가인 가교제이기 때문에 4개의 반응기를 보유하고 있는 셀룰로오스와의 반응에서 낮은 반응성으로 인하여 가교로 인한 충분한 주름방지효과를 발휘하기가 어렵게 되는 문제가 있다.However, since the non-formal glyoxal resin is a bivalent cross-linking agent used in the home textile processing method using a non-formal glyoxal resin and magnesium chloride salt as catalysts, it is low in the reaction with cellulose having four reactors. Due to the reactivity, there is a problem that it is difficult to exert a sufficient anti-wrinkle effect due to crosslinking.
따라서, 이를 해결하기 위하여, 특허문헌 1에서는 인체에 무해한 비포르말린계 글리옥살계 수지를 필수성분으로 하여 물에 분산시킨 가정용 섬유처리제 조성물에 있어서, 비포르말린계수지로서 0.3 내지 50중량%의 1,3-디메틸-4,5-디하이드록시-2-이미다졸리디논과 0.1 내지 15중량%의 반응성을 향상시키기 위한 촉매 및 0.1 내지 10중량%의 반발탄성력과 유연성이 우수한 고분자 수지를 포함하고 필요에 따라 폴리카르복시산을 이용한 에스테르형 가교제가 0.1 내지 20중량%가 함유되어 이루어지는 셀룰로오스계 의류의 수축 및 주름방지용 처리제 조성물을 제안하였으나, 이 역시 세탁 및 세탁 후 건조 시에 치수변화 방지 성능 및 형태 유지력이 매우 미비한 문제점이 있었다.Therefore, in order to solve this, in Patent Document 1, in the household fiber treatment agent composition in which non-formalin glyoxal-based resin, which is harmless to the human body, is dispersed in water as an essential component, 0.3 to 50% by weight of non-formalin-based resin, 1, Contains 3-dimethyl-4,5-dihydroxy-2-imidazolidinone and a catalyst for improving the reactivity of 0.1 to 15% by weight, and a polymer resin excellent in resilience and flexibility of 0.1 to 10% by weight According to the ester-type crosslinking agent using polycarboxylic acid, a treatment agent composition for preventing shrinkage and wrinkles of cellulose-based clothing, which contains 0.1 to 20% by weight, was proposed. There were very few problems.
본 발명은 상술한 문제점을 해결하기 위한 것으로, PPG(polypropylene glycol), PEG(polyethylene glycol) 및 PCL(polycaprolactone)이 혼합된 폴리올과 이온성기, 이소시아네이트, 쇄연장제 등을 이용하여 폴리우레탄을 합성하고 이를 이용하여 섬유 가공제를 제조함으로써, 포르말린 등의 유해 성분을 배제한 비포르말린 타입이면서도 치수변화 방지 성능이 우수할 뿐만 아니라, 섬유 원단의 유연성(softness)을 유지할 수 있도록 함을 과제로 한다.The present invention is to solve the above-mentioned problems, and synthesizes polyurethane by using polyol mixed with polypropylene glycol (PPG), polyethylene glycol (PEG) and polycaprolactone (PCL), and an ionic group, isocyanate, chain extender, etc. By manufacturing the fiber processing agent using this, it is a non-formalin type excluding harmful components such as formalin, and has an excellent performance in preventing dimensional change, as well as maintaining the softness of the fiber fabric.
아울러, 본 발명은 상기와 같이 이루어지는 폴리우레탄계 섬유 가공제를 이용하여 섬유를 가공함에 있어, 원단에 단순 코팅하는 것이 아니라, 특정 온도 및 시간 동안 이루어지는 가공 조건에서 폴리우레탄계 섬유 가공제가 섬유에 대한 결합력을 나타내어(미반응된 NCO기가 섬유 원단에 코팅되어 가공조건에서 섬유 원단과 결합하거나 물과 반응하여 가교를 형성함), 세탁 및 세탁 후 건조 시에도 치수 변화가 없고 형태 유지력이 우수하며, 특히 세탁 및 건조 시에 물 분자의 존재에 따라 수소결합 유무가 결정되므로 일시적인 결합력이 아닌 섬유의 치수(형태)를 완전히 고정시킬 수 있는 우레탄 결합을 갖도록 함을 과제로 한다.In addition, the present invention is to process the fiber using the polyurethane-based fiber processing agent made as described above, rather than a simple coating on the fabric, the polyurethane-based fiber processing agent is the binding force to the fiber under processing conditions made for a specific temperature and time Indicated (unreacted NCO groups are coated on fiber fabrics and combined with fiber fabrics under processing conditions or reacted with water to form crosslinks), there is no dimensional change during washing and drying after washing, and excellent shape retention, especially washing and washing When drying, the presence or absence of hydrogen bonds is determined according to the presence of water molecules, so the task is to have a urethane bond capable of completely fixing the dimension (shape) of the fiber rather than a temporary bonding force.
본 발명은 섬유 가공제용 폴리우레탄 수지의 제조방법에 있어서, 폴리올, 이온성기 및 용매를 투입하고 촉매를 첨가하여 혼합한 후, 여기에 이소시아네이트를 투입하여 프리폴리머를 제조하는 단계(S100); 상기 제조된 프리폴리머에 쇄연장제를 첨가하는 단계(S200); 중화제를 첨가 및 중화반응시켜 폴리우레탄을 합성하고, 여기에 용매를 추가 첨가하는 단계(S300);를 포함하여 이루어지되, 상기 폴리올은 PPG(polypropylene glycol), PEG(polyethylene glycol) 및 PCL(polycaprolactone)을 혼합하여 이루어지는 것을 특징으로 하는, 내구성이 우수한 섬유 가공제용 폴리우레탄 수지의 제조방법 및 이 방법에 의해 제조된 섬유 가공제용 폴리우레탄 수지를 과제의 해결 수단으로 한다.In the present invention, in a method for producing a polyurethane resin for a fiber processing agent, a polyol, an ionic group and a solvent are added, a catalyst is added and mixed, and then isocyanate is added thereto to prepare a prepolymer (S100); Adding a chain extender to the prepared prepolymer (S200); Synthesis of polyurethane by adding and neutralizing a neutralizing agent, and adding a solvent therein (S300); but the polyol is made of PPG (polypropylene glycol), PEG (polyethylene glycol) and PCL (polycaprolactone). A method for producing a polyurethane resin for a textile processing agent having excellent durability, characterized in that it is made by mixing, and a polyurethane resin for a textile processing agent produced by the method are used as solutions for the problems.
한편, 본 발명은 상기 제조방법에 의해 제조된 섬유 가공제용 폴리우레탄 수지 100 중량부에 대하여, 촉매 0.1 ~ 0.5 중량부 및 유연제 1 ~ 3 중량부로 이루어지는 것을 특징으로 하는 폴리우레탄계 섬유 가공제를 과제의 다른 해결 수단으로 한다.On the other hand, the present invention is a polyurethane-based fiber processing agent characterized in that it consists of 0.1 to 0.5 parts by weight of catalyst and 1 to 3 parts by weight of softener, based on 100 parts by weight of polyurethane resin for fiber processing agent produced by the above-described manufacturing method. Use another solution.
또한, 본 발명은 상기와 같이 이루어지는 폴리우레탄계 섬유 가공제를 섬유원단에 패딩처리 한 후, 170 ~ 190℃에서 1 ~ 5분간 경화시키는 것을 특징으로 하는 섬유 가공방법을 과제의 또 다른 해결 수단으로 한다.In addition, the present invention is another method for solving the problem of the fiber processing method characterized in that the polyurethane-based fiber processing agent made as described above is padded to the fiber fabric and then cured at 170 to 190 ° C for 1 to 5 minutes. .
본 발명은 포르말린 등의 유해 성분을 배제한 비포르말린 타입이면서도 세탁 및 세탁 후 건조 시에 치수변화 방지 성능이 우수할 뿐만 아니라, 섬유 원단의 유연성을 유지할 수 있도록 하는 효과를 가진다.The present invention is a non-formalin type excluding harmful components such as formalin, and has an effect of maintaining dimensional change prevention during washing and drying after washing, as well as maintaining flexibility of fiber fabrics.
도 1은 본 발명에 따른 내구성이 우수한 섬유 가공제용 폴리우레탄 수지의 제조방법을 나타낸 공정 흐름도1 is a process flow diagram showing a method of manufacturing a polyurethane resin for a textile processing agent having excellent durability according to the present invention
상기의 효과를 달성하기 위한 본 발명은 내구성이 우수한 섬유 가공제용 폴리우레탄 수지의 제조방법, 이 방법에 의해 제조된 섬유 가공제용 폴리우레탄 수지, 이를 이용하여 제조되는 폴리우레탄계 섬유 가공제 및 이 폴리우레탄계 섬유 가공제를 이용한 섬유 가공방법에 관한 것으로서, 본 발명의 기술적 구성을 이해하는데 필요한 부분만이 설명되며 그 이외 부분의 설명은 본 발명의 요지를 흩트리지 않도록 생략될 것이라는 것을 유의하여야 한다.The present invention for achieving the above effect is a method for producing a polyurethane resin for a textile processing agent having excellent durability, a polyurethane resin for a textile processing agent produced by the method, a polyurethane-based fiber processing agent manufactured using the same, and this polyurethane-based It should be noted that as for a method for processing a fiber using a fiber processing agent, only parts necessary for understanding the technical configuration of the present invention are described, and descriptions of other parts will be omitted so as not to distract the subject matter of the present invention.
이하, 본 발명에 따른 내구성이 우수한 섬유 가공제용 폴리우레탄 수지의 제조방법 및 이 방법에 의해 제조된 섬유 가공제용 폴리우레탄 수지를 상세히 설명하면 다음과 같다.Hereinafter, a method of manufacturing a polyurethane resin for a textile processing agent having excellent durability according to the present invention and a polyurethane resin for a textile processing agent produced by the method will be described in detail as follows.
본 발명은 도 1에 도시된 바와 같이, 프리폴리머를 제조하는 단계(S100), 쇄연장제 및 블록킹제를 첨가하는 단계(S200) 및 중화반응단계(S300)를 포함하여 이루어진다.As shown in FIG. 1, the present invention comprises a step of preparing a prepolymer (S100), a step of adding a chain extender and a blocking agent (S200) and a step of neutralizing reaction (S300).
상기 S100 단계는, 폴리올, 이온성기 및 용매를 투입하고 촉매를 첨가하여 혼합한 후, 여기에 이소시아네이트를 투입하여 프리폴리머를 제조하는 단계로써, 용매 245 중량부에 대하여, 폴리올 40 ~ 70 중량부 및 이온성기 1 ~ 10 중량부를 투입하고 50 ~ 80℃로 승온한 후, 촉매 0.001 ~ 0.1 중량부를 첨가하여 40 ~ 80℃에서 혼합하고, 여기에 이소시아네이트 32 ~ 33 중량부를 투입하고 60 ~ 90℃에서 60 ~ 300분간 합성하여 프리폴리머를 제조한다. 여기서 상기 각 물질의 함량 및 제조 조건이 상기 범위를 벗어날 경우 치수변화 방지 성능 및 형태 유지력이 미비하거나 또는 프리폴리머가 제대로 제조되지 못할 우려가 있다.In the step S100, a polyol, an ionic group and a solvent are added, a catalyst is added and mixed, and then isocyanate is added thereto to prepare a prepolymer, with respect to 245 parts by weight of the solvent, 40 to 70 parts by weight of polyol and ions 1 to 10 parts by weight of the penis is added and heated to 50 to 80 ° C, then 0.001 to 0.1 parts by weight of the catalyst is added and mixed at 40 to 80 ° C, 32 to 33 parts by weight of isocyanate is added thereto, and 60 to 90 ° C at 60 to 90 ° C Synthesized for 300 minutes to prepare a prepolymer. Here, if the content and manufacturing conditions of each material are out of the above range, there is a fear that the dimensional change prevention performance and shape retention force are insufficient or the prepolymer cannot be properly produced.
한편, 본 발명에서 상기 폴리올은PPG(polypropylene glycol) 20 ~ 30 중량%, PEG(polyethylene glycol) 40 ~ 60 중량% 및 PCL(polycaprolactone) 20 ~ 30 중량%을 혼합하여 이루어지는 것을 사용하며, 상기 함량 범위를 벗어날 경우 치수변화 방지 성능 및 형태 유지력이 미비해질 우려가 있다.On the other hand, in the present invention, the polyol is composed of 20 to 30% by weight of polypropylene glycol (PPG), 40 to 60% by weight of PEG (polyethylene glycol) and 20 to 30% by weight of PCL (polycaprolactone), and the content range If it deviates from, there is a concern that the dimensional change prevention performance and shape retention power may be insufficient.
아울러, 상기 이온성기는, n-MDEA(n-methyldiethanolamine), n-BDEA(n-butyldiethanolamine), TBDEA(n-t-butyldiethanolamine), MDPA(n-methyldipropanolamine) 또는 MDIPA(n-methyldiisopropanolamine)를 사용한다.In addition, the ionic group, n-methyldiethanolamine (n-MDEA), n-butyldiethanolamine (n-BDEA), n-t-butyldiethanolamine (TBDEA), n-methyldipropanolamine (MDPA) or n-methyldiisopropanolamine (MDIPA) is used.
또한, 용매는 메틸에틸케톤(methylethylketone,MEK), 디메틸포름아미드(dimethylformamide, DMF) 또는 톨루엔(Toluene) 중에서 단독 또는 2종 이상 병용하여 사용하고, 촉매는 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL)를 사용한다.In addition, the solvent is methylethylketone (methylethylketone, MEK), dimethylformamide (dimethylformamide, DMF) or toluene (Toluene) alone or in combination of two or more, the catalyst is used for dibutyltin dilaurate (dibutyltin dilaurate, DBTDL) Use
그리고, 이소시아네이트는 HDI(Hexamethylene diisocyanate), MDI(Methylene Diphenyl Diisocyanate), TDI(Toluene Diisocyanate), IPDI(Isophorone Diisocyanate), H12MDI(dicyclohexylmethane diisocyanate), TMXDI(Tetramethylxylene Diisocyanate), NDI(naphthalene-1,5-diisocyanate), XDI(m-xylene diisocyanate), CHDI(1,4-cyclohexyl diisocyanate) 또는 DDI(Diphenylmethane diisocyanate)의 둘 이상의 이성질체, 다이머, 트라이머, 및 혼합물 또는 조합물를 적용한다.And, the isocyanate is HDI (Hexamethylene diisocyanate), MDI (Methylene Diphenyl Diisocyanate), TDI (Toluene Diisocyanate), IPDI (Isophorone Diisocyanate), H12MDI (dicyclohexylmethane diisocyanate), TMXDI (Tetramethylxylene Diisocyanate), NDI (naphthalene-1,5-diisocyanate) ), Two or more isomers, dimers, trimers, and mixtures or combinations of m-xylene diisocyanate (XDI), 1,4-cyclohexyl diisocyanate (CHDI) or diphenylmethane diisocyanate (DDI) are applied.
한편, 상기 이소시아네이트와 폴리올의 당량비가 1.0 : 0.99 ~ 1.0 : 0.85가 바람직하며, 이 범위를 벗어날 경우 프리폴리머가 제대로 제조되지 못할 우려가 있다.On the other hand, the equivalent ratio of the isocyanate and the polyol is preferably 1.0: 0.99 to 1.0: 0.85, and if it is outside this range, there is a fear that the prepolymer cannot be properly produced.
상기 S200 단계는, 상기 제조된 프리폴리머에 쇄연장제를 혼합하고, 블록킹제를 첨가하는 단계로써, 상기 제조된 프리폴리머 100 중량부에 대하여, 쇄연장제 5 ~ 15 중량부를 혼합하고 60 ~ 90℃에서 30 ~ 300분간 합성한 후, 블록킹제 1 ~ 5 중량부를 첨가한다. 여기서 쇄연장제 및 블록킹제의 함량 및 제조 조건이 상기 범위를 벗어날 경우, 폴리우레탄이 제대로 합성되지 못할 우려가 있다.The step S200 is a step of mixing a chain extender with the prepared prepolymer, and adding a blocking agent. With respect to 100 parts by weight of the prepared prepolymer, 5 to 15 parts by weight of chain extender are mixed and at 60 to 90 ° C. After 30 to 300 minutes of synthesis, 1 to 5 parts by weight of blocking agent is added. Here, if the content of the chain extender and the blocking agent and the manufacturing conditions are outside the above range, there is a fear that the polyurethane may not be properly synthesized.
여기서, 상기 쇄연장제는 EG(ethyleneglycol), DEG(diethyleneglycol), 1,4-BD(ButaneDiol), NPG(Neopentylglycol), 1,6-HD(HexaneDiol), CHDM(Dimethylcyclohexanedimethylol), 1,12-DD(DodecaneDiol) 등의 다이올계와 피페라진(Piperazine), 히드라진(Hydrazine), IPDA(Isophorone diamine), HMDA(hexamethylenediamine), EDA(Ethylene diamine) 등 다이아민계 중에서 단독 또는 2종 이상 선택하여 사용하고, 상기 블록킹제(blocking agent)는 2-부타논 옥심(2-butanone oxime), 이미다졸(imidazole), 1,2,4-트리아졸(1,2,4-triazole), 2-부타아닌디에틸말로네이트(2-butanine diethyl malonate), 에틸아세트아세테이트(ethylacetoacetate) 또는 메틸에틸케톡심(methylethyl ketoxime) 중에서 단독 또는 2종 이상을 혼합하여 사용한다.Here, the chain extender is EG (ethyleneglycol), DEG (diethyleneglycol), 1,4-BD (ButaneDiol), NPG (Neopentylglycol), 1,6-HD (HexaneDiol), CHDM (Dimethylcyclohexanedimethylol), 1,12-DD (DodecaneDiol) such as diol-based and piperazine (Piperazine), hydrazine (Hydrazine), IPDA (Isophorone diamine), HMDA (hexamethylenediamine), EDA (Ethylene diamine), etc., alone or two or more selected from the diamine system is used, Blocking agents include 2-butanone oxime, imidazole, 1,2,4-triazole, and 2-butanine diethylmalo. It is used alone or in combination of two or more of 2-butanine diethyl malonate, ethylacetoacetate or methylethyl ketoxime.
상기 S300 단계는, 중화제를 첨가 및 중화반응시켜 폴리우레탄을 합성하고, 여기에 용매를 추가 첨가하는 단계로써, 상기 S200 단계 후, 온도를 30 ~ 70℃로 하고 프리폴리머 100 중량부에 대하여, 중화제 2 ~ 3 중량부를 첨가하여 60 ~ 180분간 중화시켜 반응을 종료하고, 용매 45 ~ 55 중량부를 추가 첨가한다. 이때 상기 각 물질의 함량 및 제조 조건이 상기 범위를 벗어날 경우 중화반응이 제대로 이루어지지 않을 우려가 있다.The step S300 is a step of adding and neutralizing a neutralizing agent to synthesize polyurethane, and further adding a solvent thereto, after the step S200, the temperature is 30 to 70 ° C. and the prepolymer is 100 parts by weight, and the neutralizing agent 2 The reaction was terminated by adding ~ 3 parts by weight to neutralize for 60 to 180 minutes, and additionally added 45 to 55 parts by weight of the solvent. At this time, if the content and manufacturing conditions of each material are outside the above range, there is a fear that the neutralization reaction may not be properly performed.
상기 사용되는 중화제는 아세트산(acetic acid), 포름산(formic acid), 글리콜산(glycolic acid) 등의 유기산 또는 염산(HCl) 등을 사용할 수 있다.As the neutralizing agent used, organic acids such as acetic acid, formic acid, and glycolic acid or hydrochloric acid (HCl) may be used.
다음으로, 상기와 같이 제조된 섬유 가공제용 폴리우레탄 수지를 이용하여 제조되는 폴리우레탄계 섬유 가공제 및 이 폴리우레탄계 섬유 가공제를 이용한 섬유 가공방법를 상세히 설명하면 다음과 같다.Next, the polyurethane-based fiber processing agent prepared using the polyurethane resin for the fiber processing agent prepared as described above and the fiber processing method using the polyurethane-based fiber processing agent will be described in detail as follows.
본 발명에 따른 폴리우레탄계 섬유 가공제는, 상기와 같이 제조된 섬유 가공제용 폴리우레탄 수지 100 중량부에 대하여, 촉매 0.1 ~ 0.5 중량부 및 유연제 1 ~ 3 중량부로 이루어진다.The polyurethane-based fiber processing agent according to the present invention is made of 0.1 to 0.5 parts by weight of the catalyst and 1 to 3 parts by weight of the catalyst with respect to 100 parts by weight of the polyurethane resin for the fiber processing agent prepared as described above.
여기서, 상기 촉매는 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL)를 사용하며, 상기 유연제는 폴리실록산 에멀젼(polysiloxane emulsion)과 같은 실리콘게 유연제 등을 사용할 수 있다. 한편, 상기 촉매 및 유연제의 함량이 상기 범위를 벗어날 경우, 섬유 가공제용 폴리우레탄 수지에 의한 치수변화 방지 성능 및 형태 유지력 향상 효율이 저하될 우려가 있다.Here, the catalyst uses dibutyltin dilaurate (DBTDL), and the softener may be a silicone crab softener such as a polysiloxane emulsion. On the other hand, when the content of the catalyst and the softener is out of the above range, there is a fear that the dimensional change prevention performance and the shape retention power improvement efficiency by the polyurethane resin for the fiber processing agent may be deteriorated.
아울러, 본 발명에 따른 섬유 가공방법은 상기와 같이 이루어지는 폴리우레탄계 섬유 가공제를 섬유원단에 패딩(padding, 섬유 원단에 섬유 가공제를 묻히는 공정)처리 한 후, 170 ~ 190℃에서 1 ~ 5분간 경화시킨다. 여기서 상기 온도 및 시간이 상기 범위를 벗어날 경우 섬유 가공제와 섬유의 결합력이 미비해질 우려가 있다.In addition, the fiber processing method according to the present invention is a polyurethane-based fiber processing agent made as described above (padding, the process of applying a fiber processing agent to the fiber fabric) after treatment, 170 ~ 190 ℃ for 1 ~ 5 minutes Harden. Here, if the temperature and time are out of the above range, there is a fear that the bonding force between the fiber processing agent and the fiber becomes insufficient.
이하, 본 발명의 실시 예를 들면서 상세히 설명하는 바 본 발명이 다음의 실시예에 의해서만 반드시 한정되는 것은 아니다. Hereinafter, the present invention will be described in detail by way of example, but the present invention is not necessarily limited to the following examples.
1. 섬유 가공제용 폴리우레탄 수지의 제조1. Preparation of polyurethane resins for textile processing agents
(제조예 1)(Production Example 1)
교반기, 환류 냉각기, 질소 주입구가 장착된 4구 반응기(2L)에 용매(MEK) 245 중량부에 대하여, 수분이 제거된 PPG 20 중량%, PEG 60 중량% 및 PCL 20 중량%을 혼합한 혼합 폴리올 40 중량부 및 이온성기(n-MDEA) 1 중량부를 투입하고 50℃로 승온한 후, 촉매(DBTDL) 0.001 중량부를 첨가하여 80℃에서 혼합하고, 여기에 이소시아네이트(HDI) 32 중량부를 투입(이소시아네이트와 폴리올의 당량비 1.0 : 0.85)하고 60℃에서 60분간 합성하여 프리폴리머를 제조한다(S100). 그리고 상기 제조된 프리폴리머 100 중량부에 대하여, 쇄연장제(EG) 5 중량부 및 블록킹제(2-부타논 옥심) 1 중량부를 첨가하고 60℃에서 NCO 피크가 소멸될때 까지 30분간 합성한다(S200). 이후, 온도를 30℃로 하고 프리폴리머 100 중량부에 대하여, 중화제(아세트산) 2 중량부를 첨가하여 60분간 중화시켜 반응을 종료하고, 용매(MEK) 45 중량부를 추가 첨가(S300)하여 섬유 가공제용 폴리우레탄 수지를 제조하였다.A mixed polyol mixed with 20% by weight of PPG, 60% by weight of PEG and 20% by weight of PCL, based on 245 parts by weight of solvent (MEK) in a 4-neck reactor (2L) equipped with a stirrer, reflux cooler, and nitrogen inlet. After adding 40 parts by weight and 1 part by weight of ionic group (n-MDEA) and heating to 50 ° C, 0.001 part by weight of catalyst (DBTDL) is added and mixed at 80 ° C, and 32 parts by weight of isocyanate (HDI) is added thereto (isocyanate And polyol equivalent ratio 1.0: 0.85) and synthesized at 60 ° C. for 60 minutes to prepare a prepolymer (S100). Then, with respect to 100 parts by weight of the prepolymer prepared, 5 parts by weight of a chain extender (EG) and 1 part by weight of a blocking agent (2-butanone oxime) are added and synthesized for 30 minutes at 60 ° C until the NCO peak disappears (S200). ). Thereafter, the temperature was set to 30 ° C., and 2 parts by weight of a neutralizing agent (acetic acid) was added to neutralize for 60 minutes with respect to 100 parts by weight of the prepolymer, and the reaction was terminated by adding 45 parts by weight of a solvent (MEK) (S300). Urethane resins were prepared.
(제조예 2)(Production Example 2)
교반기, 환류 냉각기, 질소 주입구가 장착된 4구 반응기(2L)에 용매(MEK) 245 중량부 중량부에 대하여, 수분이 제거된 PPG 30 중량%, PEG 40 중량% 및 PCL 30 중량%을 혼합한 혼합 폴리올 70 중량부 및 이온성기(n-MDEA) 10 중량부를 투입하고 80℃로 승온한 후, 촉매(DBTDL) 0.1 중량부를 첨가하여 40℃에서 혼합하고, 여기에 이소시아네이트(HDI) 33 중량부를 투입(이소시아네이트와 폴리올의 당량비 1.0 : 0.99)하고 90℃에서 300분간 합성하여 프리폴리머를 제조한다(S100). 그리고 상기 제조된 프리폴리머 100 중량부에 대하여, 쇄연장제(DEG) 15 중량부 및 블록킹제(이미다졸) 5 중량부를 첨가하고 90℃에서 NCO 피크가 소멸될때 까지 300분간 합성한다(S200). 이후, 온도를 70℃로 하고 프리폴리머 100 중량부에 대하여, 중화제(포름산) 3 중량부를 첨가하여 180분간 중화시켜 반응을 종료하고, 용매(MEK) 55 중량부를 추가 첨가(S300)하여 섬유 가공제용 폴리우레탄 수지를 제조하였다.Stirrer, reflux cooler, nitrogen inlet, a 4-neck reactor (2L) equipped with 245 parts by weight of solvent (MEK), based on 245 parts by weight of moisture removed PPG 30% by weight, PEG 40% by weight and PCL 30% by weight After adding 70 parts by weight of the mixed polyol and 10 parts by weight of the ionic group (n-MDEA) and heating to 80 ° C, 0.1 parts by weight of the catalyst (DBTDL) is added and mixed at 40 ° C, and 33 parts by weight of isocyanate (HDI) is added thereto. (Equivalent ratio of isocyanate and polyol 1.0: 0.99) and synthesized at 90 ° C. for 300 minutes to prepare a prepolymer (S100). And with respect to 100 parts by weight of the prepolymer prepared, 15 parts by weight of a chain extender (DEG) and 5 parts by weight of a blocking agent (imidazole) are added and synthesized for 300 minutes at 90 ° C. until the NCO peak disappears (S200). Thereafter, the temperature was set to 70 ° C., and 3 parts by weight of a neutralizing agent (formic acid) was added to neutralize the reaction for 180 minutes by adding 3 parts by weight of a neutralizing agent (formic acid), and 55 parts by weight of a solvent (MEK) was further added (S300) to produce poly for the fiber processing agent. Urethane resins were prepared.
2. 폴리우레탄계 섬유 가공제의 제조2. Manufacturing of polyurethane-based fiber processing agent
(실시예 1)(Example 1)
제조예 1에 따른 섬유 가공제용 폴리우레탄 수지 100 중량부에 대하여, 촉매(DBTDL) 0.1 중량부 및 유연제(폴리실록산 에멀젼) 1 중량부를 혼합하여 폴리우레탄계 섬유 가공제를 제조하였다.With respect to 100 parts by weight of the polyurethane resin for a fiber processing agent according to Preparation Example 1, 0.1 parts by weight of a catalyst (DBTDL) and 1 part by weight of a softener (polysiloxane emulsion) were mixed to prepare a polyurethane-based fiber processing agent.
(실시예 2)(Example 2)
제조예 2에 따른 섬유 가공제용 폴리우레탄 수지 100 중량부에 대하여, 촉매(DBTDL) 0.5 중량부 및 유연제(폴리실록산 에멀젼) 3 중량부를 혼합하여 폴리우레탄계 섬유 가공제를 제조하였다.With respect to 100 parts by weight of the polyurethane resin for a fiber processing agent according to Preparation Example 2, 0.5 parts by weight of a catalyst (DBTDL) and 3 parts by weight of a softener (polysiloxane emulsion) were mixed to prepare a polyurethane-based fiber processing agent.
(비교예 1)(Comparative Example 1)
특허문헌 1을 참조하여, 1,3-디메틸-4,5-디하이드록시-2-이미다졸리디논 20 중량%, 염화마그네슘 6 중량%, 실리콘-우레탄 공중합체 수지(우레탄 100 중량부에 대하여 아미노 실리콘 10 중량부 혼합) 3 중량% 및 정제수 71 중량%를 혼합하여 섬유 가공제를 제조하였다.With reference to Patent Document 1, 1,3-dimethyl-4,5-dihydroxy-2-imidazolidinone 20% by weight, magnesium chloride 6% by weight, silicone-urethane copolymer resin (with respect to 100 parts by weight of urethane Mixing 10 parts by weight of amino silicone) 3% by weight and 71% by weight of purified water were prepared to prepare a fiber processing agent.
3. 폴리우레탄계 섬유 가공제의 평가3. Evaluation of polyurethane-based fiber processing agent
상기 실시예 및 비교예에 따라 제조된 섬유 가공제를 면 섬유(가로 50cm x 세로 50cm)에 패딩처리한 후, 180℃에서 2분간 경화시켜 시험편을 제조하였으며, 상기 시험편에 대한 세탁 후 치수변화율을 평가(KS K 0465(직물 및 편성물의 수축률 시험방법))하고, 그 결과를 아래 [표 1]에 나타내었다.The fiber processing agent prepared according to the above Examples and Comparative Examples was padded with cotton fibers (50 cm x 50 cm) and cured at 180 ° C. for 2 minutes to prepare test specimens. Evaluation (KS K 0465 (fabric and knitted fabric shrinkage test method)), the results are shown in [Table 1] below.
상기 [표 1]에서와 같이, 본 발명에 따른 실시예 1, 2의 경우, 비교예 1에 비하여 치수변화 방지 성능 및 형태 유지력 등의 내구성이 우수함을 알 수 있다.As shown in [Table 1], it can be seen that Examples 1 and 2 according to the present invention have superior durability, such as dimensional change prevention performance and shape retention power, compared to Comparative Example 1.
상술한 바와 같은, 본 발명의 바람직한 실시예에 따른 내구성이 우수한 섬유 가공제용 폴리우레탄 수지의 제조방법, 이 방법에 의해 제조된 섬유 가공제용 폴리우레탄 수지, 이를 이용하여 제조되는 폴리우레탄계 섬유 가공제 및 이 폴리우레탄계 섬유 가공제를 이용한 섬유 가공방법을 상기한 설명 및 도면에 따라 설명하였지만 이는 예를 들어 설명한 것에 불과하며 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 변화 및 변경이 가능하다는 것을 이 분야의 통상적인 기술자들은 잘 이해할 수 있을 것이다.As described above, a method for manufacturing a polyurethane resin for a textile processing agent having excellent durability according to a preferred embodiment of the present invention, a polyurethane resin for a textile processing agent produced by the method, a polyurethane-based textile processing agent produced using the same, and Although the fiber processing method using the polyurethane-based fiber processing agent has been described in accordance with the above description and drawings, this is merely an example, and it is possible that various changes and changes are possible without departing from the technical spirit of the present invention. Ordinary technicians will be able to understand well.
Claims (11)
폴리올, 이온성기 및 용매를 투입하고 촉매를 첨가하여 혼합한 후, 여기에 이소시아네이트를 투입하여 프리폴리머를 제조하는 단계(S100);
상기 제조된 프리폴리머에 쇄연장제를 혼합하고, 블록킹제를 첨가하는 단계(S200);
중화제를 첨가 및 중화반응시켜 폴리우레탄을 합성하고, 여기에 용매를 추가 첨가하는 단계(S300);를 포함하여 이루어지되,
상기 폴리올은 PPG(polypropylene glycol), PEG(polyethylene glycol) 및 PCL(polycaprolactone)을 혼합하여 이루어지며,
상기 S100 단계는 용매 245 중량부에 대하여, 폴리올 40 ~ 70 중량부 및 이온성기 1 ~ 10 중량부를 투입하고 50 ~ 80℃로 승온한 후, 촉매 0.001 ~ 0.1 중량부를 첨가하여 40 ~ 80℃에서 혼합하고, 여기에 이소시아네이트 32 ~ 33 중량부를 투입하고 60 ~ 90℃에서 60 ~ 300분간 합성하여 프리폴리머를 제조하되, 상기 폴리올은 PPG 20 ~ 30 중량%, PEG 40 ~ 60 중량% 및 PCL 20 ~ 30 중량%을 혼합하여 이루어지고,
상기 S100 단계는 이소시아네이트와 폴리올의 당량비가 1.0 : 0.99 ~ 1.0 : 0.85이며,
상기 S200 단계는 상기 제조된 프리폴리머 100 중량부에 대하여, 쇄연장제 5 ~ 15 중량부를 혼합하고 60 ~ 90℃에서 30 ~ 300분간 합성한 후, 블록킹제 1 ~ 5 중량부를 첨가하고,
상기 S300 단계는 상기 S200 단계 후, 온도를 30 ~ 70℃로 하고 프리폴리머 100 중량부에 대하여, 중화제 2 ~ 3 중량부를 첨가하여 60 ~ 180분간 중화시켜 반응을 종료하고, 용매 45 ~ 55 중량부를 추가 첨가하며,
상기 이온성기는 n-MDEA(n-methyldiethanolamine), n-BDEA(n-butyldiethanolamine), TBDEA(n-t-butyldiethanolamine), MDPA(n-methyldipropanolamine) 또는 MDIPA(n-methyldiisopropanolamine)을 사용하고,
상기 이소시아네이트는 HDI(Hexamethylene diisocyanate), MDI(Methylene Diphenyl Diisocyanate), TDI(Toluene Diisocyanate), IPDI(Isophorone Diisocyanate), H12MDI(dicyclohexylmethane diisocyanate), TMXDI(Tetramethylxylene Diisocyanate), NDI(naphthalene-1,5-diisocyanate), XDI(m-xylene diisocyanate), CHDI(1,4-cyclohexyl diisocyanate) 또는 DDI(Diphenylmethane diisocyanate) 중에서 단독 또는 2종 이상을 혼합하여 사용하며,
상기 블록킹제는 2-부타논 옥심(2-butanone oxime), 이미다졸(imidazole), 1,2,4-트리아졸(1,2,4-triazole), 2-부타아닌디에틸말로네이트(2-butanine diethyl malonate), 에틸아세트아세테이트(ethylacetoacetate) 또는 메틸에틸케톡심(methylethyl ketoxime) 중에서 단독 또는 2종 이상을 혼합하여 사용하는 것을 특징으로 하는, 내구성이 우수한 섬유 가공제용 폴리우레탄 수지의 제조방법.
In the manufacturing method of the polyurethane resin for textile processing agents,
After the polyol, an ionic group and a solvent are added and a catalyst is added and mixed, an isocyanate is added thereto to prepare a prepolymer (S100);
Mixing a chain extender with the prepared prepolymer and adding a blocking agent (S200);
Synthesis of polyurethane by adding and neutralizing the neutralizing agent, and adding a solvent therein (S300);
The polyol is made by mixing polypropylene glycol (PPG), polyethylene glycol (PEG) and polycaprolactone (PCL),
In the step S100, 40 to 70 parts by weight of polyol and 1 to 10 parts by weight of ionic group are added to 245 parts by weight of the solvent, and the temperature is raised to 50 to 80 ° C, and then 0.001 to 0.1 parts by weight of catalyst is added and mixed at 40 to 80 ° C. Then, 32 to 33 parts by weight of isocyanate was added thereto and synthesized at 60 to 90 ° C. for 60 to 300 minutes to prepare a prepolymer, wherein the polyol was 20 to 30% by weight of PPG, 40 to 60% by weight of PEG, and 20 to 30% by weight of PCL. % By mixing,
In step S100, the equivalent ratio of isocyanate and polyol is 1.0: 0.99 to 1.0: 0.85,
In step S200, 5 to 15 parts by weight of a chain extender is mixed with respect to 100 parts by weight of the prepared prepolymer, synthesized at 60 to 90 ° C for 30 to 300 minutes, and then 1 to 5 parts by weight of a blocking agent is added,
In the step S300, after the step S200, the temperature is set to 30 to 70 ° C., and 2 to 3 parts by weight of a neutralizing agent is added to neutralize 60 to 180 minutes to terminate the reaction by adding 2 to 3 parts by weight of a prepolymer, and 45 to 55 parts by weight of a solvent is added. Add,
The ionic group uses n-methyldiethanolamine (n-MDEA), n-butyldiethanolamine (n-BDEA), nt-butyldiethanolamine (TBDEA), n-methyldipropanolamine (MDPA) or n-methyldiisopropanolamine (MDIPA),
The isocyanate is HDI (Hexamethylene diisocyanate), MDI (Methylene Diphenyl Diisocyanate), TDI (Toluene Diisocyanate), IPDI (Isophorone Diisocyanate), H12MDI (dicyclohexylmethane diisocyanate), TMXDI (Tetramethylxylene Diisocyanate), NDI (naphthalene-1,5-diisocyanate) , XDI (m-xylene diisocyanate), CHDI (1,4-cyclohexyl diisocyanate) or DDI (Diphenylmethane diisocyanate), alone or in combination of two or more.
The blocking agent is 2-butanone oxime, imidazole, 1,2,4-triazole, 2-butanine diethylmalonate (2 A method for producing a polyurethane resin for a textile processing agent having excellent durability, characterized in that it is used alone or in combination of two or more of butanine diethyl malonate, ethylacetoacetate, or methylethyl ketoxime.
Polyurethane resin for textile processing agent manufactured by the manufacturing method according to claim 1.
A polyurethane-based fiber processing agent, characterized in that it comprises 0.1 to 0.5 parts by weight of catalyst and 1 to 3 parts by weight of softener, based on 100 parts by weight of polyurethane resin for textile processing agent according to claim 9.
After the padding treatment of the polyurethane-based fiber processing agent according to claim 10 on the fiber fabric, characterized in that curing for 1 to 5 minutes at 170 ~ 190 ℃, fiber processing method.
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