KR101068270B1 - Synthesis and application of urethane acrylate for breathable water proof textiles as UV fixing agent - Google Patents
Synthesis and application of urethane acrylate for breathable water proof textiles as UV fixing agent Download PDFInfo
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- KR101068270B1 KR101068270B1 KR1020090093175A KR20090093175A KR101068270B1 KR 101068270 B1 KR101068270 B1 KR 101068270B1 KR 1020090093175 A KR1020090093175 A KR 1020090093175A KR 20090093175 A KR20090093175 A KR 20090093175A KR 101068270 B1 KR101068270 B1 KR 101068270B1
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- urethane acrylate
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- moisture
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 39
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 42
- 239000004753 textile Substances 0.000 title description 3
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- 239000000835 fiber Substances 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000003672 processing method Methods 0.000 claims abstract description 11
- -1 poly (dimethylsiloxane) Polymers 0.000 claims description 30
- 238000004078 waterproofing Methods 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims description 19
- 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 18
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 16
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 229920001451 polypropylene glycol Polymers 0.000 claims description 13
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229920005862 polyol Polymers 0.000 claims description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- 125000004386 diacrylate group Chemical group 0.000 claims description 6
- XCLIHDJZGPCUBT-UHFFFAOYSA-N dimethylsilanediol Polymers C[Si](C)(O)O XCLIHDJZGPCUBT-UHFFFAOYSA-N 0.000 claims description 6
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000012754 barrier agent Substances 0.000 claims description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 19
- 238000012545 processing Methods 0.000 abstract description 11
- 238000003848 UV Light-Curing Methods 0.000 abstract description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000005871 repellent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 241000190070 Sarracenia purpurea Species 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000028016 temperature homeostasis Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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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
- 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
-
- 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
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/001—Treatment with visible light, infrared or ultraviolet, X-rays
-
- 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
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
- D06M10/10—Macromolecular compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/345—Nitriles
- D06M13/348—Nitriles unsaturated, e.g. acrylonitrile
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
-
- 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
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/02—Moisture-responsive characteristics
- D10B2401/021—Moisture-responsive characteristics hydrophobic
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
본 발명은 UV 경화형 투습방수용 우레탄 아크릴레이트 조성물 및 이를 이용한 섬유의 가공 처리방법에 관한 것으로서, 더욱 상세하게는 화학식 1로 표시되는 실록산을 포함하는 수평균 분자량이 5,000 ~ 20,000의 우레탄 아크릴레이트와 화학식 2로 표시되는 수평균 분자량이 5,000 ~ 20,000의 우레탄 아크릴레이트가 특정 조성비로 혼합되어 제반견뢰도가 우수하고 투습방수력이 높은 우레탄 아크릴레이트 조성물, 이 조성물을 함유하는 투습방수제 및 이를 이용한 섬유의 가공 처리방법에 관한 것이다.The present invention relates to a UV-curable moisture-permeable waterproof urethane acrylate composition and a processing method of fibers using the same, and more particularly, a urethane acrylate having a number average molecular weight of 5,000 to 20,000 including a siloxane represented by Formula 1 and Formula 2 A urethane acrylate composition having a number average molecular weight of 5,000 to 20,000 is mixed in a specific composition ratio to provide excellent urethane acrylate composition with high fastness and moisture permeability and moisture permeability, and a moisture permeable waterproof agent containing the composition and a method for processing fibers using the same. It is about.
UV 경화, 투습방수, 우레탄 아크릴레이트 UV curing, moistureproof, urethane acrylate
Description
본 발명은 UV 경화형 투습방수용 우레탄 아크릴레이트 조성물, 이 조성물을 함유하는 투습방수제 및 이를 이용한 섬유의 가공 처리방법에 관한 것이다.The present invention relates to a UV-curable moisture-permeable urethane acrylate composition, a moisture-repellent waterproofing agent containing the composition, and a fiber processing method using the same.
일반적으로 섬유에 원하는 투습성과 방수성이 우수한 가공포를 얻기 위해서는, 중합체 사슬 중에 친수성 부분을 도입하거나 저투습성 수지에 고투습성의 친수성 수지를 혼합하여 용제에 녹인 후 섬유에 코팅한다. 건조 및 고온 열 처리를 통해 가공제액을 섬유에 고착시킴으로 에너지 소비가 많으며 유기용제의 사용으로 VOC(Volatile Organic Compounds)가 많이 생성되는 문제점을 갖는다. 따라서, 최근 섬유에 가공제를 경화시키기 위한 수단으로서 UV 조사에 의한 경화를 이용하는 기술이 도입되었다. In general, in order to obtain a fabric having excellent desired moisture permeability and water resistance to the fiber, a hydrophilic portion is introduced into the polymer chain, or a high moisture-permeable hydrophilic resin is mixed with a low moisture-permeable resin and dissolved in a solvent and then coated on the fiber. There is a problem in that energy consumption is high by fixing the processing agent liquid to the fiber through drying and high temperature heat treatment, and VOC (Volatile Organic Compounds) is generated by using an organic solvent. Therefore, the technique which uses hardening by UV irradiation was introduced in recent years as a means for hardening a processing agent to a fiber.
섬유용 UV 경화 가공기술 개발은 에너지용수 사용량 및 폐수 발생량을 현저히 줄일 수 있는 미래형 최첨단 염색가공 기술로 ① 열 건조. 열 경화에 비하여 경 화 시간이 짧아 생산성이 좋고, ② 휘발용재가 적어 환경 저부하형(환경 대응형 수지)인 점, ③ 특히, UV 경화는 설비가 콤팩트(compact)하여 면적이 적게 필요하고 설비 투자가 작은 것을 장점이 있으나, 반대로 단점은 ① 열 경화형의 종래의 수지 조성에 비하여 단가가 높고, ② 비교적 작은 분자량의 상태로부터 단시간에 급속히 경화시키기 때문에 가교점이 많고, 그 때문에 경화 수축이 커서 경화물 깨짐과 밀착 불량이 일어나기 쉽고, ③ 용제 사용으로 인한 피부 자극을 유발한다. 특히, 기존에 도료, 잉크, 전자 재료에 사용되는 UV 경화제를 섬유에 적용할 경우 이런 단점이 더욱 부각된다. 섬유의 물성을 손상시키지 않고, 투습 방수성이 우수한 섬유를 제공하기 위한 UV 경화를 이용한 가공법에 관한 연구가 요구되는 실정이다. The development of UV curing processing technology for textiles is a future state-of-the-art dyeing and processing technology that can significantly reduce energy consumption and wastewater generation. ① Thermal drying. Productivity is good due to short curing time compared to heat curing. ② Environmentally low load type (environmental resin) due to less volatile materials. ③ Especially UV curing requires small area due to compact equipment and investment in equipment. However, the disadvantage is that the cost is higher than the conventional resin composition of the thermosetting type. Over-adhesion is likely to occur, ③ cause skin irritation due to the use of solvents. In particular, when applying a UV curing agent to the fibers conventionally used in paints, inks, electronic materials, these disadvantages are more highlighted. There is a need for a study on a processing method using UV curing to provide a fiber having excellent moisture permeability and water resistance without impairing the physical properties of the fiber.
이에, 본 발명자들은 상기와 같은 문제점을 해결하기 위하여 연구 노력한 결과, 다음 화학식 1로 표시되는 수평균 분자량이 5,000 ~ 20,000의 우레탄 아크릴레이트와, 다음 화학식 2로 표시되는 수평균 분자량이 5,000 ~ 20,000의 우레탄 아크릴레이트로 구성된 UV 경화형 투습방수용 우레탄 아크릴레이트 조성물을 개발함으로써 본 발명을 완성하게 되었다. Thus, the inventors of the present invention, in order to solve the problems described above, the number average molecular weight represented by the following formula (1) is 5,000 to 20,000 urethane acrylate and the number average molecular weight represented by the following formula (2) of 5,000 to 20,000 The present invention has been completed by developing a urethane acrylate composition for UV curing moisture permeable waterproof composed of urethane acrylate.
[화학식 1][Formula 1]
상기 화학식 1에서, P는 수평균 분자량이 1,000 ~ 4,000의 폴리에틸렌글리콜 또는 폴리프로필렌글리콜/폴리에틸렌글리콜이고, S는 수평균 분자량이 550 ~ 4,000의 하이드록시 말단화 폴리(디메틸실록산)[Poly(dimethylsiloxane) hydroxy terminated]이며, D는 IPDI(Isophorone diisocyanate), TMXDI(m-Tetramethylxylylene diisocyanate) 또는 H12MDI(4,4‘-Dicyclohexyl-methane diisocyanate)이다.In Chemical Formula 1, P is polyethylene glycol or polypropylene glycol / polyethylene glycol having a number average molecular weight of 1,000 to 4,000, and S is a hydroxy-terminated poly (dimethylsiloxane) having a number average molecular weight of 550 to 4,000 [Poly (dimethylsiloxane) hydroxy terminated], and D is Isophorone diisocyanate (IPDI), m- Tetramethylxylylene diisocyanate (TMXDI) or H 12 MDI (4,4'-Dicyclohexyl-methane diisocyanate).
[화학식 2][Formula 2]
상기 화학식 1에서, F는 수평균 분자량이 1,000 ~ 4,000의 폴리테트라메틸렌글리콜 또는 카프로락톤계 폴리올이며, I는 DMPA(Dimethylol propionic acid) 또는 DMBA(Dimethylol butyric acid)이고, D는 IPDI, TMXDI 또는 H12MDI이다.In Formula 1, F is a polytetramethylene glycol or caprolactone polyol having a number average molecular weight of 1,000 to 4,000, I is dimethylol propionic acid (DMPA) or dimethylol butyric acid (DMBA), and D is IPDI, TMXDI, or H. 12 MDI.
따라서, 본 발명은 실록산을 포함하는 우레탄 아크릴레이트 조성물, 이를 포함하는 투습방수제를 제공하는데 그 목적으로 있다. Accordingly, an object of the present invention is to provide a urethane acrylate composition comprising a siloxane, and a moisture-permeable waterproof agent comprising the same.
또한, 본 발명은 용제를 사용하지 않고 수계화가 가능한 상기 투습방수제를 이용하여, 섬유에 투습방수성을 부여하는 가공 처리방법을 제공하는데 또 다른 목적이 있다. Another object of the present invention is to provide a processing method for imparting water-permeable waterproofness to fibers using the water-permeable waterproof agent that can be water-based without using a solvent.
본 발명은 The present invention
다음 화학식 1로 표시되는 수평균 분자량이 5,000 ~ 20,000의 우레탄 아크릴레이트와, 다음 화학식 2로 표시되는 수평균 분자량이 5,000 ~ 20,000의 우레탄 아크릴레이트로 구성된 UV 경화형 투습방수용 우레탄 아크릴레이트 조성물을 그 특징으로 한다;A urethane acrylate composition having a number average molecular weight of 5,000 to 20,000 represented by the following Chemical Formula 1 and a urethane acrylate having a number average molecular weight of 5,000 to 20,000 represented by the following Chemical Formula 2 is characterized by do;
[화학식 1][Formula 1]
상기 화학식 1에서, P는 수평균 분자량이 1,000 ~ 4,000의 폴리에틸렌글리콜 또는 폴리프로필렌글리콜/폴리에틸렌글리콜이고, S는 수평균 분자량이 550 ~ 4,000의 하이드록시 말단화 폴리(디메틸실록산)[Poly(dimethylsiloxane) hydroxy terminated]이며, D는 IPDI(Isophorone diisocyanate), TMXDI(m-Tetramethylxylylene diisocyanate) 또는 H12MDI(4,4‘-Dicyclohexyl-methane diisocyanate)이다.In Chemical Formula 1, P is polyethylene glycol or polypropylene glycol / polyethylene glycol having a number average molecular weight of 1,000 to 4,000, and S is a hydroxy-terminated poly (dimethylsiloxane) having a number average molecular weight of 550 to 4,000 [Poly (dimethylsiloxane) hydroxy terminated], and D is Isophorone diisocyanate (IPDI), m- Tetramethylxylylene diisocyanate (TMXDI) or H 12 MDI (4,4'-Dicyclohexyl-methane diisocyanate).
[화학식 2][Formula 2]
상기 화학식 1에서, F는 수평균 분자량이 1,000 ~ 4,000의 폴리테트라메틸렌글리콜 또는 카프로락톤계 폴리올이며, I는 DMPA(Dimethylol propionic acid) 또는 DMBA(Dimethylol butyric acid)이고, D는 IPDI, TMXDI 또는 H12MDI이다.In Formula 1, F is a polytetramethylene glycol or caprolactone polyol having a number average molecular weight of 1,000 to 4,000, I is dimethylol propionic acid (DMPA) or dimethylol butyric acid (DMBA), and D is IPDI, TMXDI, or H. 12 MDI.
또한, 본 발명은In addition,
상기 우레탄 아크릴레이트 조성물 100 중량부, 광개시제 1 ~ 4 중량부 및 가교보조제 2 ~ 5 중량부를 포함하는 투습방수제를 또 다른 특징으로 한다. The water-permeable waterproof agent comprises 100 parts by weight of the urethane acrylate composition, 1 to 4 parts by weight of a photoinitiator and 2 to 5 parts by weight of a crosslinking aid.
또한, 본 발명은, In addition, the present invention,
투습방수성을 부여할 섬유 시료에 상기 투습방수제를 코팅하는 단계;Coating the moisture permeable on a fiber sample to impart moisture permeability;
코팅된 섬유 시료에 UV를 조사하여 상기 투습방수제가 섬유 시료 표면에 경화되는 단계;Irradiating the coated fiber sample with UV to cure the water vapor barrier on the surface of the fiber sample;
를 포함하는 섬유의 가공 처리방법을 또 다른 특징으로 한다.It is another feature of the processing method of the fiber comprising a.
본 발명의 투습방수제를 이용한 섬유의 가공 처리방법에 의하면, 열에 의한 섬유 손상을 방지할 수 있으므로 가공제를 섬유에 고착시킨 후에도 해당 섬유의 고유의 특성을 유지할 수 있고, 형태 안정성을 유지할 수 있다. 본 발명의 섬유의 가공 처리방법은 환경 오염이나 인체에 악영향을 미칠 우려가 없고, 종래의 열경화 장치에 비하여 설치 면적을 적게 차지할 뿐 아니라 고온의 열이 요구되지 아니하므로 보다 경제적으로 투습방수성을 제공할 수 있다. According to the processing method of the fiber using the moisture-permeable waterproofing agent of the present invention, it is possible to prevent fiber damage due to heat, so that even after the processing agent is fixed to the fiber, the inherent properties of the fiber can be maintained and shape stability can be maintained. The processing method of the fiber of the present invention has no risk of environmental pollution or adverse effects on the human body, and it provides economical moisture-permeable waterproofing because it takes up less installation area and does not require high temperature heat as compared with the conventional thermosetting device. can do.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 우수한 투습방수성을 가지고 있는 다음 화학식 1로 표시되는 실록산을 포함하는 수평균 분자량이 5,000 ~ 20,000의 우레탄 아크릴레이트와 다음 화학식 2로 표시되는 수평균 분자량이 5,000 ~ 20,000의 우레탄 아크릴레이트 조성물, 이 조성물을 함유하는 투습방수제 및 이를 이용한 섬유의 가공 처리방법에 관한 것이다;The present invention has a urethane acrylate having a number average molecular weight of 5,000 to 20,000 and a urethane acrylate composition having a number average molecular weight of 5,000 to 20,000 represented by the following formula (2) comprising a siloxane represented by the following formula (1) having excellent moisture-permeable waterproof, It is related with the moisture-permeable waterproofing agent containing this composition, and the processing method of the fiber using the same;
[화학식 1][Formula 1]
상기 화학식 1에서, P는 수평균 분자량이 1,000 ~ 4,000의 폴리에틸렌글리콜 또는 폴리프로필렌글리콜/폴리에틸렌글리콜이고, S는 수평균 분자량이 550 ~ 4,000의 하이드록시 말단화 폴리(디메틸실록산)[Poly(dimethylsiloxane) hydroxy terminated]이며, D는 IPDI, TMXDI 또는 H12MDI이다.In Chemical Formula 1, P is polyethylene glycol or polypropylene glycol / polyethylene glycol having a number average molecular weight of 1,000 to 4,000, and S is a hydroxy-terminated poly (dimethylsiloxane) having a number average molecular weight of 550 to 4,000 [Poly (dimethylsiloxane) hydroxy terminated], D is IPDI, TMXDI or H 12 MDI.
[화학식 2][Formula 2]
상기 화학식 2에서, F는 수평균 분자량이 1,000 ~ 4,000의 폴리테트라메틸렌글리콜 또는 카프로락톤계 폴리올이며, I는 DMPA 또는 DMBA이고, D는 IPDI, TMXDI 또는 H12MDI이다.In Formula 2, F is a polytetramethylene glycol or caprolactone polyol having a number average molecular weight of 1,000 to 4,000, I is DMPA or DMBA, and D is IPDI, TMXDI, or H 12 MDI.
상기 화학식 1의 화합물은 IPDI, TMXDI, H12MDI와 같은 이소시아네이트에 폴리올, 반응성 폴리디메틸실록산, 아크릴레이트 반응기를 반응시키며, 상기 화학식 2의 화합물은 이소시아네이트와 PTMG 등 소수성 폴리올을 반응시켜 제조할 수 있다. The compound of Formula 1 may be prepared by reacting a polyol, a reactive polydimethylsiloxane, an acrylate reactor with an isocyanate such as IPDI, TMXDI, H 12 MDI, and the compound of Formula 2 may be prepared by reacting a hydroisocyanate with a hydrophobic polyol such as PTMG. .
또한, 본 발명은 상기 화학식 1의 화합물과 화학식 2의 화합물을 혼합한 우레탄 아크릴레이트 조성물 100 중량부에 대하여, 광개시제 1 ~ 4 중량부 및 가교보조제 2 ~ 5 중량부를 포함하는 투습방수제를 포함한다. 이때, 조성물은 화학식 1의 화합물과 화학식 2의 화합물을 10 ~ 50 : 50 ~ 90의 중량비로 혼합한 것이 바람직하다. 상기 혼합비의 범위를 벗어나면 투습성과 방수성이 불량해지는 문제가 있다.In addition, the present invention comprises a moisture-permeable waterproofing agent containing 1 to 4 parts by weight of the photoinitiator and 2 to 5 parts by weight of the crosslinking assistant with respect to 100 parts by weight of the urethane acrylate composition of the compound of Formula 1 and the compound of Formula 2. At this time, the composition is preferably a mixture of the compound of Formula 1 and the compound of Formula 2 in a weight ratio of 10 to 50:50 to 90. If the mixing ratio is out of the range, there is a problem in that moisture permeability and water resistance are poor.
광개시제는 UV가 조사되면 여기되어 라디칼 또는 이온을 발생하게 하여 광중합을 개시하거나 또는 다른 증감제의 도움으로 광중합을 일으키는 작용을 하며, 바람직하기로는 벤조페논계 화합물, 아실 포스핀 옥사이드 화합물, 아세토페논계 화합물 및 벤조인 에테르계 화합물 중에서 선택된 1종 이상이 적합하다. 바람직하게는 2-하이드록시-2-메틸프로피온페논, 1-하이드록시 사이클로헥실케탈, 디페닐-(2,4,6-트리메틸벤조일) 포스핀 옥사이드 등을 사용하며, 보다 바람직하게는 2-하이드록시-2-메틸프로피온페논과 디페닐-(2,4,6-트리메틸벤조일) 포스핀 옥사이드을 혼합하여 사용한다. The photoinitiator is excited when UV is irradiated to generate radicals or ions to initiate photopolymerization or to cause photopolymerization with the aid of other sensitizers, preferably a benzophenone compound, an acyl phosphine oxide compound, or an acetophenone compound. At least one selected from the group consisting of compounds and benzoin ether compounds is suitable. Preferably 2-hydroxy-2-methylpropionphenone, 1-hydroxy cyclohexyl ketal, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide and the like are used, more preferably 2- Hydroxy-2-methylpropionphenone and diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide are used in combination.
상기 광개시제는 상기 화학식 1의 화합물과 화학식 2의 화합물을 혼합한 우 레탄 아크릴레이트 조성물 100 중량부에 대하여 1 ~ 4 중량부 사용된다. 이때 광개시제의 함량이 1 중량부 미만이면 경화도가 저하되어 투습방수성이 나빠지고, 4 중량부 초과 사용해도 경화도 증가에 도움이 안 된다.The photoinitiator is used in an amount of 1 to 4 parts by weight based on 100 parts by weight of the urethane acrylate composition in which the compound of Formula 1 and the compound of Formula 2 are mixed. At this time, when the content of the photoinitiator is less than 1 part by weight, the degree of curing is lowered, and the moisture permeability is worse.
가교보조제는 투습방수성 증가 및 투습방수제의 점도조절 역할을 하며 디아크릴레이트를 포함하는 모노머를 사용한다. 바람직하게는 실리콘 아크릴레이트, PEG 400으로 제조된 디아크릴레이트 등을 사용하며, 보다 바람직하게는 PEG 400으로 제조된 디아크릴레이트를 사용한다. The crosslinking aid serves to increase moisture permeability and to control viscosity of the moisture permeable waterproofing agent, and uses a monomer including diacrylate. Preferably, silicone acrylate, diacrylate made of PEG 400, or the like is used, and more preferably diacrylate made of PEG 400 is used.
상기 가교보조제는 상기 화학식 1의 화합물과 화학식 2의 화합물을 혼합한 우레탄 아크릴레이트 조성물 100 중량부에 대하여 2 ~ 5 중량부 사용된다. 2 중량부 미만이면 가교보조제의 역할을 못하며, 5 중량부를 초과하면 투습방수제의 기능을 저하시킨다.The crosslinking assistant is used in an amount of 2 to 5 parts by weight based on 100 parts by weight of the urethane acrylate composition in which the compound of Formula 1 and the compound of Formula 2 are mixed. Less than 2 parts by weight does not act as a crosslinking aid, and if more than 5 parts by weight reduces the function of the moisture-permeable waterproof agent.
이러한 투습방수제는 상기 성분 이외에 공지의 소광제, 증점제, 광분해 안정제 등을 첨가제로 더 포함할 수도 있다.Such moisture-permeable waterproofing agent may further include a known matting agent, thickener, photolysis stabilizer, etc. in addition to the above components.
본 발명에 따른 투습방수제는 투습도가 3,000 ~ 7,000g/m2 24 hr이고, 내수압이 1,000 ~ 8,000 mmH2O으로서, 기존 열경화 투습방수제와 유사한 효과를 가진다.The moisture-permeable waterproofing agent according to the present invention has a water vapor transmission rate of 3,000 to 7,000 g / m 2 24 hr and a water pressure of 1,000 to 8,000 mmH 2 O, and has an effect similar to that of a conventional thermosetting water-repellent waterproofing agent.
또한, 본 발명은 In addition,
투습방수성을 부여할 섬유 시료에 상기 투습방수제를 코팅하는 단계; 및Coating the moisture permeable on a fiber sample to impart moisture permeability; And
상기 코팅된 섬유 시료에 UV를 조사하여 상기 투습방수제를 섬유 시료 표면에 경화시키는 단계Irradiating the coated fiber sample with UV to cure the moisture-permeable waterproofing agent on the surface of the fiber sample
를 포함하여 이루어진 섬유의 가공 처리방법을 포함한다.It includes a processing method of the fiber comprising a.
이때, 사용되는 섬유 시료는 천연섬유와 합성섬유 모두 사용할 수 있으며, 직물, 편물 및 부직포도 투습방수 처리의 대상이 될 수 있다. At this time, the fiber sample used can be used both natural fibers and synthetic fibers, woven fabrics, knitted fabrics and non-woven fabrics may also be subject to the waterproofing treatment.
UV는 가시광선보다 짧은 파장을 가진 전자파로서 조사 파장에 따라 조사표면 유기물의 분자결합을 절단하고 산화시킬 수 있을 뿐 아니라 용이하게 광경화성 모노머를 중합 및 가교화시킬 수 있다.UV is an electromagnetic wave having a wavelength shorter than visible light, and can not only cut and oxidize molecular bonds of the irradiated surface organic material depending on the irradiation wavelength but also easily polymerize and crosslink the photocurable monomer.
이러한 UV의 방출은 전자파를 방출하기 쉬운 원자구조를 갖는 물질을 가열하여 증기 상태로 만들고 동시에 외부로부터 큰 에너지를 가함으로써 이루어진다. 대표적으로 수은램프를 많이 사용하는데 수은 기체원자가 에너지를 받으면 수은 전자가 들뜨게 되고 그 후 전자가 안정된 상태로 돌아가면서 우리 눈에 보이지 않는 UV를 방출하게 된다. 일반적으로 UV 램프는 살균용 및 UV 경화용 등으로 나누어지며 방사되는 에너지의 세기와 파장의 범위에 따라 용도별로 다양하게 사용되고 있다.The emission of UV is achieved by heating a substance having an atomic structure that is easy to emit electromagnetic waves to vaporize and applying a large amount of energy from the outside. Typically, mercury lamps are used a lot. When a mercury gas atom receives energy, mercury electrons are excited, and then the electrons return to a stable state to emit invisible UV. In general, UV lamps are divided into sterilization and UV curing, and are used in various ways depending on the intensity and wavelength range of the emitted energy.
UV 경화를 이용한 섬유의 가공방법에 있어서, UV 경화 메커니즘은 라디칼 반응과 양이온 반응으로 크게 구분할 수 있다. 라디칼 반응의 경우 UV에 의해 가공제에 포함된 광개시제가 활성화되어 자유 라디칼이 생성되고, 생성된 라디칼은 다시 반응형 올리고머를 활성화시켜 거대한 망상 구조를 형성시킨 다음, 정지 반응을 통해 경화 반응이 종료되어 가공이 완료된다.In the fiber processing method using UV curing, the UV curing mechanism can be largely divided into radical reaction and cationic reaction. In the case of the radical reaction, the photoinitiator included in the processing agent is activated by UV to generate free radicals, which in turn activate the reactive oligomer to form a huge network structure, and then the curing reaction is terminated through a stop reaction. Machining is completed.
본 발명에서는 섬유 시료를 상기 UV경화형 투습방수제로 코팅시킨 후 60 ~ 100 ℃에서 약 1 ~ 5분간 건조 과정을 거친다. 건조 과정을 거침으로써 경화반 응의 효율을 보다 향상시킬 수 있다. In the present invention, the fiber sample is coated with the UV-curable moisture-permeable waterproofing agent and then dried for about 1 to 5 minutes at 60 to 100 ° C. The drying process can further improve the efficiency of the curing reaction.
이때, 코팅은 롤 온 나이프나 그라비아를 이용하여 코팅하며, 코팅 두께는 20 ~ 50 ㎛ 되도록 함이 바람직하다. 코팅 두께가 20 ㎛ 미만이면 부가되는 투습방수제 양이 적어 투습방수도가 저하되고, 50 ㎛를 초과하면 과량의 투습방수제로 섬유 촉감이 뻣뻣하여 피막이 깨질 수 있다. At this time, the coating is coated using a roll-on knife or gravure, the coating thickness is preferably 20 to 50 ㎛. If the coating thickness is less than 20 µm, the amount of moisture-permeable waterproof agent added is low, and the moisture-permeable waterproofness is lowered.
특히, 본 발명에 따른 투습방수제를 섬유 시료에 코팅 시 투습방수제의 코팅량이 15 ~ 50 g/m2가 바람직하며, 이 범위를 벗어나면 물성이나 촉감에 문제가 있다. In particular, when the moisture-permeable waterproofing agent according to the present invention is coated on a fiber sample, the coating amount of the moisture-permeable waterproofing agent is preferably 15 to 50 g / m 2 , and there is a problem in physical properties and feel.
이후 UV 조사기를 이용하여 건조된 시료에 UV를 조사한다. 가공제의 경화를 위한 UV 조사에는 주파장이 UV-A 영역인 금속할로겐 램프나 갈륨 램프를 사용함이 바람직하다. Thereafter, UV is irradiated to the dried sample using a UV irradiator. It is preferable to use a metal halogen lamp or a gallium lamp whose main wavelength is UV-A region for UV irradiation for hardening of a processing agent.
UV 조사량은 섬유의 투습방수도에 영향을 미치는데, 0.5 ~ 2 J/cm2 범위에서 조사함이 바람직하고, 더욱 바람직하게는 1.0 ~ 1.5 J/cm2 범위로 조사한다. 0.5 J/cm2 미만이면 광개시제의 활성화가 잘 이루어지지 않아 경화 반응의 진행이 활발하지 않게 되어 투습방수도가 떨어지는 문제가 있으며, 2 J/cm2를 초과하면 섬유가 취화된다. The amount of UV radiation affects the moisture permeability of the fiber, from 0.5 to 2 J / cm 2 Irradiation in the range is preferred, more preferably 1.0 to 1.5 J / cm 2 Investigate by range. 0.5 J / cm 2 If it is less than the activation of the photoinitiator is not made well, the progress of the curing reaction is not active there is a problem that the moisture-permeable waterproofness is falling, when exceeding 2 J / cm 2 fibers are embrittled.
이하, 본 발명은 다음 실시예에 의거하여 구체적으로 설명하겠는 바, 본 발 명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail based on the following examples, but the present invention is not limited thereto.
참조예Reference Example : : NCONCO 측정 Measure
250 ml 삼각 플라스크에 시료를 2 ~ 3 g 채취하였다. 톨루엔 25 ml을 가하여 용해(톨루엔에 용해되지 않을시 이소프로판올 사용가능)시켰다. 2N n-디부틸아민([CH3(CH2)3] 2NH = 129.25,1L, Assay:99%) 용액 20 ml 피펫으로 가하였다. 15 ~ 20분 방치 후, 이소프로판올 100 ml를 메스실린더로 가하였다. 브로크레솔 그린(Bromocresol green) 지시약을 약 5 ~ 10 방울 가한 후, 1N 염산 수용액으로 적정 시작하였다. 2 g 브로크레솔 그린(C21H13Br4O5SNa=720:시약명)을 에탄올에 녹여 100 ml 되게 하였다. 청색에서 황색으로 변할 때를 종말점으로 하고 동시에 공시험을 수행하였다. 2-3 g of the sample was taken in a 250 ml Erlenmeyer flask. 25 ml of toluene was added to dissolve (isopropanol can be used when not dissolved in toluene). A 20 ml pipette of 2N n-dibutylamine ([CH 3 (CH 2 ) 3 ] 2 NH = 129.25,1 L, Assay: 99%) solution was added. After standing for 15-20 minutes, 100 ml of isopropanol was added to the measuring cylinder. After adding about 5-10 drops of Bromocresol green indicator, titration was started with 1N aqueous hydrochloric acid solution. 2 g Brocresol Green (C 21 H 13 Br 4 O 5 SNa = 720: Name of reagent) was dissolved in ethanol to make 100 ml. A blank test was performed at the end of the transition from blue to yellow.
[수학식 1][Equation 1]
NCO % = [(A-B) X F x 4.2] / SNCO % = [(AB) XF x 4.2] / S
A : 공시험의 1N 염산수용액의 사용량 A: Amount of 1N aqueous hydrochloric acid solution
B : 본시험의 1N 염산수용액의 사용량B: amount of 1N aqueous hydrochloric acid solution
F : 1N 염산 수용액의 농도 계수 F: concentration coefficient of 1N hydrochloric acid aqueous solution
S : 시료의 무게 (g)S: sample weight (g)
제조예Manufacturing example 1 : 화학식 1a의 화합물 제조 1: Preparation of Compound of Formula 1a
500 ml 4-네크 플라스크에 메카니컬(mechanical) 교반기, 건조 튜브가 연결된 콘덴서, 온도계 및 질소 투입장치를 장착하였다. 상기 장착된 플라스크를 맨틀(mantle)에 넣고 먼저 플라스크 안을 진공 상태에서 가열하여 잔여 수분을 제거하였다. 선정된 PEG/PPG(Mn 1,000 ~ 4,000), Poly(dimethylsiloxane) hydroxy terminated(Mn 550 ~ 4,000)을 평량한 후 플라스크에 투입하였다. 0.1%(w/w) 촉매(dibutyl tin dilaurate)가 들어있는 IPDI(외 TMXDI나 H12MDI 사용 가능)를 천천히 적가(발열반응)하고 적가가 모두 완결되면 75 ~ 80 ℃로 승온시켰다(NCO : OH 비율 = 1.4~1.8:1). 승온 후 2시간부터 NCO 함량을 측정하면서 예상 함량이 나오면(4 ~ 5%) 50 ℃로 냉각하고 NCO 말단을 캡핑하기 위한 2-하이드록시에틸 아크릴레이트 반응기를 도입하였다. 반응 진행은 NCO 측정법이나 FT-IR로 확인하면서[도 1 참조] NCO 특성 피크인 2270 cm-1 피크가 사라지면 물로 30 ~ 40% 고형분이 되게 농도 조절을 하였다. The 500 ml 4-neck flask was equipped with a mechanical stirrer, a condenser with a drying tube, a thermometer and a nitrogen input. The mounted flask was placed in a mantle and the flask was first heated in vacuo to remove residual moisture. The selected PEG / PPG (Mn 1,000 ~ 4,000), Poly (dimethylsiloxane) hydroxy terminated (Mn 550 ~ 4,000) was weighed and added to the flask. IPDI containing 0.1% (w / w) catalyst (dibutyl tin dilaurate) (other than TMXDI or H 12 MDI can be used) was slowly added dropwise (exothermic reaction) and the temperature was raised to 75 ~ 80 ℃ (NCO: OH ratio = 1.4-1.8: 1). After measuring the NCO content from 2 hours after the increase in temperature (4-5%) when the expected content comes to introduce a 2-hydroxyethyl acrylate reactor for cooling to 50 ℃ and capping the NCO end. Reaction progress was confirmed by NCO measurement or FT-IR (see FIG. 1), and the concentration was adjusted to 30 to 40% solids with water when the NCO characteristic peak 2270 cm -1 peak disappeared.
다음 화학식 1a로 표시되는 우레탄 아크릴레이트를 제조하였다(수평균 분자량이 1,000인 폴리프로필렌글리콜/폴리에틸렌글리콜과 수평균 분자량이 550인 하이드록시 말단화 폴리(디메틸실록산)을 사용한 경우, 수평균 분자량: 6,880); The urethane acrylate represented by Formula 1a was prepared (when polypropylene glycol / polyethylene glycol having a number average molecular weight of 1,000 and hydroxy-terminated poly (dimethylsiloxane) having a number average molecular weight of 550) was used, the number average molecular weight was 6,880. );
[화학식 1a][Formula 1a]
상기 화학식 1a에서, P는 수평균 분자량이 1,000 ~ 4,000의 폴리프로필렌글리콜/폴 리에틸렌글리콜이고, S는 수평균 분자량이 550 ~ 4,000의 하이드록시 말단화 폴리(디메틸실록산)[Poly(dimethylsiloxane) hydroxy terminated]이며, D는 IPDI(Isophorone diisocyanate)이다.In Formula 1a, P is polypropylene glycol / polyethylene glycol having a number average molecular weight of 1,000 to 4,000, and S is a hydroxy terminated poly (dimethylsiloxane) having a number average molecular weight of 550 to 4,000 [Poly (dimethylsiloxane) hydroxy terminated] and D is Isophorone diisocyanate (IPDI).
제조예Manufacturing example 2 : 화학식 2의 화합물 제조 2 Preparation of the Compound of Formula 2
500 ml 4-네크 플라스크에 메카니칼 교반기, 건조 튜브가 연결된 콘덴서, 온도계 및 질소 투입장치를 장착하였다. 상기 장착된 플라스크를 맨틀에 넣고 먼저 플라스크 안을 진공 상태에서 가열하여 잔여수분을 제거하였다. 하기 반응식 1에 따라 선정된 PTMG(Polytetramethylene glycol, Mn 1,000~4,000, 205BA(Caprolactone계 glycol)들을 평량한 후 플라스크에 투입하였다. 90 ℃에서 폴리올들을 모두 혼합한 후 60 ℃로 냉각시킨 후 DMBA(Dimethylol butyric acid) 넣고 용해시켰다. 0.1%(w/w) 촉매(dibutyl tin dilaurate)가 들어있는 IPDI를 천천히 적가(발열반응임)하고 적가가 모두 완결되면 75 ~ 80 ℃로 승온시켰다. 승온 후 2시간부터 NCO 함량을 측정하면서 예상 함량이 나오면(4 ~ 5%) 50 ℃로 냉각하고 NCO 말단을 캡핑하기 위한 아크릴 반응기(2-HEMA, 2-HEA, Glycidol)를 도입하였다. 반응 진행은 NCO 측정법이나 FT-IR로 확인하였다[도 2 참조]. 반응이 종결되면 물로 희석한 트리에틸아민을 적가하여 50 ℃에서 1시간 동안 중화하였다. 30 ~ 40% 고형분이 되게 농도 조절을 하였다.The 500 ml 4-neck flask was equipped with a mechanical stirrer, a condenser with a drying tube, a thermometer and a nitrogen injector. The mounted flask was placed in a mantle and the flask was first heated in vacuo to remove residual moisture. PTMG (Polytetramethylene glycol, Mn 1,000 ~ 4,000, 205BA (Caprolactone glycol) was selected according to Scheme 1 below was weighed and added to the flask after mixing all the polyols at 90 ℃ and cooled to 60 ℃ and then DMBA (Dimethylol butyric acid) was dissolved in. IPDI containing 0.1% (w / w) catalyst (dibutyl tin dilaurate) was slowly added dropwise (exothermic reaction) and the temperature was raised to 75-80 ° C. after completion of the dropwise addition. After measuring the NCO content (4 ~ 5%), when the expected content (4 ~ 5%) was cooled to 50 ℃ and introduced an acrylic reactor (2-HEMA, 2-HEA, Glycidol) for capping the NCO end. Confirmed by FT-IR, see Fig. 2. Upon completion of the reaction, triethylamine diluted with water was added dropwise and neutralized for 1 hour at 50 ° C. The concentration was adjusted to 30 to 40% solids.
다음 화학식 2a로 표시되는 우레탄 아크릴레이트를 제조하였다(수평균 분자량이 4,000의 폴리테트라메틸렌글리콜을 사용한 경우, 수평균 분자량 9,200); To prepare a urethane acrylate represented by the following formula (2a) (when using polytetramethylene glycol having a number average molecular weight of 4,000, the number average molecular weight 9,200);
[화학식 2a](2a)
상기 화학식 2a에서, F는 수평균 분자량이 1,000 ~ 4,000의 폴리테트라메틸렌글리콜 또는 카프로락톤계 폴리올이며, I는 DMBA(Dimethylol butyric acid)이고, D는 IPDI이다.In Formula 2a, F is a polytetramethylene glycol or caprolactone polyol having a number average molecular weight of 1,000 to 4,000, I is dimethylol butyric acid (DMBA), and D is IPDI.
[반응식 1]Scheme 1
상기 반응식 1에서, F는 폴리테트라메틸렌 글리콜 또는 카프로락톤계 글리콜, D는 이소포론 디이소시아네이트, I는 디메틸올 부티릭 에시드, R은 H 또는 메틸기이다.In Scheme 1, F is polytetramethylene glycol or caprolactone glycol, D is isophorone diisocyanate, I is dimethylol butyric acid, R is H or methyl group.
실시예Example 1 : 섬유의 투습방수제의 제조 및 가공 처리 1: Preparation and processing of moisture-permeable waterproofing agent of fiber
상기 제조예 1에서 제조한 화합물과 상기 제조예 2에서 제조한 화합물을 1 : 1의 중량비로 혼합한 우레탄 아크릴레이트 조성물 100 g, 2-하이드록시-2-메틸프로피온페논과 디페닐-(2,4,6-트리메틸벤조일) 포스핀 옥사이드를 3:1로 혼합한 광개시제 4 g 및 가교보조제로서 PEG 400으로 제조된 디아크릴레이트 5 g을 넣어 투습방수제를 제조하였다.100 g of a urethane acrylate composition obtained by mixing the compound prepared in Preparation Example 1 and the compound prepared in Preparation Example 2 in a weight ratio of 1: 1, 2-hydroxy-2-methylpropionphenone and diphenyl- (2, 4,6-trimethylbenzoyl) 4 g of a photoinitiator mixed with phosphine oxide 3: 1 and 5 g of a diacrylate made of PEG 400 as a crosslinking aid was added to prepare a water vapor barrier.
투습방수 처리할 시료로서 발수 처리된 폴리에틸렌테레프탈레이트 직물(83데시테스-36필라멘트사 중량 70 g/m2) 30cm × 20cm 크기로 잘라 준비하였고 이를 상기 희석된 투습방수제로 롤 온 나이프 코팅하였다.Water-repellent polyethylene terephthalate fabric (83 decithes-36 filament yarn weight 70 g / m 2 ) as a sample to be moisture-permeable, cut to 30cm × 20cm size prepared and roll-on knife coated with the diluted water-repellent waterproofing agent.
코팅된 시료를 80 ℃에서 2분간 건조한 다음, 메탈램프(Fe)를 장착한 UV 경화기를 이용하여 조사량을 1.1 J/cm2로 하여 UV를 조사하였다. The coated sample was dried at 80 ° C. for 2 minutes, and then irradiated with UV with a dose of 1.1 J / cm 2 using a UV curing machine equipped with a metal lamp (Fe).
투습방수 가공이 완료된 섬유 시료의 투습성과 방수성의 평가는 다음과 같은 방법으로 측정하였다.Evaluation of the moisture permeability and water resistance of the fiber sample after the water-permeable waterproofing process was measured by the following method.
1. 평가방법1. Evaluation method
(1) 투습성(KS K 0594, JIS L 1099, ASTM E 96)(1) Moisture permeability (KS K 0594, JIS L 1099, ASTM E 96)
의복을 착용할 때 인체의 체온조정 작용에 의해서 발한 시 땀의 증발에 의한 수증기는 의복을 구성하는 천, 천의 층을 통하여 수증기압이 낮은 외부로의 발산을 해야만 한다. 이때, 수증기는 천을 구성하는 실과 실 사이의 섬유와 섬유 간의 공간을 통과하지만 섬유가 친수성인 경우에는 섬유에 흡착 흡수되어 섬유 내로 들어간다. 이와 같이 천이 수증기를 통과시키는 성질을 투습성이라 하며 측정방 법에는 워터법(증발법)과 염화칼슘법, 초산칼슘법(흡수법)이 있으며, 본 발명에서는 워터법 중 인버터 워터컵법으로 측정했으며 투과된 수분의 양을 g/m2 24hr로 표시하였다When wearing clothes, the water vapor caused by the evaporation of sweat caused by the body's thermoregulation should emit to the outside with low water vapor pressure through the layers of cloth and cloth constituting the clothes. At this time, the water vapor passes through the space between the fiber and the fiber between the yarn constituting the cloth, but when the fiber is hydrophilic, it is absorbed and absorbed by the fiber and enters the fiber. As such, the property of passing the transition water vapor is called moisture permeability, and the measurement method includes water method (evaporation method), calcium chloride method, calcium acetate method (absorption method), and in the present invention, the water method is measured by the inverter water cup method and transmitted. The amount of water was expressed in g / m 2 24hr.
(2) 방수도 (내수압 KS K 5091/ ISO 811/ JIS L 1092)(2) Waterproof degree (waterproof pressure KS K 5091 / ISO 811 / JIS L 1092)
시험편 표면에 물방울이 3개 보이기 시작할 때의 수위를 mm 단위로 나타냄. Shows the water level in mm when three droplets start to appear on the specimen surface.
물의 누수 또는 침수에 대한 직물의 저항성을 내수도라고 하며 우의, 우산지, 천막지 등 방수가공직물의 방수 정도를 측정하기 위한 시험이다. 의류용이나 산업재료로 사용되는 섬유제품 중에서 방수성, 방우성, 투수성 등 용도에 따라 여러 가지 형태의 물에 대한 저항성이 요구되며 시험 방법도 각기 다르며, 단위는 mmH2O로 표시하였다.The resistance of fabrics to water leakage or submersion is called water resistance and is a test to measure the degree of waterproofing of waterproof fabrics such as raincoats, umbrellas, and tents. In textile products for use in clothes or industrial materials in accordance with the water resistance, room dominant, permeability, etc. use is required resistance to a number of different forms of water, each test method also, a unit is expressed in mmH 2 O.
투습방수 처리된 섬유와 미처리된 섬유는 내수압에서 크게 차이가 남을 확인할 수 있었다. The moisture-repellent and non-treated fibers were significantly different in the water pressure.
[표 1]TABLE 1
(mmH2O)Water pressure
(mmH 2 O)
실시예Example 2 : 투습방수 가공제의 분자구조에 따른 2: according to the molecular structure of the moisture-permeable waterproofing agent 투습방수성Breathable 측정 Measure
상기 실시예 1과 동일하게 섬유 가공 처리를 하되, 이소시아네이트의 종류를 달리하며 투습방수 처리를 한 뒤, 이에 따른 투습방수도를 측정하여 이를 다음 표 2에 나타내었다. The fiber processing was performed in the same manner as in Example 1, but after the moisture-permeable waterproof treatment was performed with different kinds of isocyanates, the moisture-permeable waterproof degree was measured and shown in Table 2 below.
[표 2]TABLE 2
g/m2 24 hr Breathable
g / m 2 24 hr
mmH2OWater pressure
mmH 2 O
분자구조에 변화에 따른 투습방수력이 크게 차이가 났으며 3종의 이소시아네이트 중 IPDI(Isophorone diisocyanate)가 반응할 때도 점도도 증가되지 않고 투습방수성도 우수하였다.The moisture permeability was significantly different due to the change in molecular structure. The viscosity was not increased and the moisture permeability was excellent even when IPDI (Isophorone diisocyanate) among the three isocyanates reacted.
실시예Example 3 : 3: 코팅막Coating film 두께에 따른 According to thickness 내수압Water pressure 측정 Measure
투습방수제에서 첨가되는 물의 양을 조절하여 희석된 농도를 달리하면서 코팅막 두께를 조절하여 방수도를 측정하였고, 이를 다음 표 3에 나타내었다. The water resistance was measured by controlling the thickness of the coating film while varying the diluted concentration by controlling the amount of water added in the moisture-permeable waterproofing agent, which is shown in Table 3 below.
[표 3][Table 3]
(후도계로 측정)Coating film thickness (㎛)
(Measured with a colorimeter)
(mmH2O)Water pressure
(mmH 2 O)
상기 표 3과 같이, 코팅막 두께가 증가할수록 방수도는 좋아지나 코팅막 두께가 50 ㎛를 초과하면 섬유가 뻣뻣해져 촉감이 나빠지는 것을 확인하였다. As shown in Table 3, as the coating film thickness increases, the waterproofness is improved, but when the coating film thickness exceeds 50 μm, the fiber is stiff and it was confirmed that the touch is worse.
실시예Example 4 : 4 : 광개시제의Photoinitiator 농도에 따른 According to concentration 내수압Water pressure 측정 Measure
상기 실시예 1의 우레탄 아크릴레이트 조성물 100 g에 대한 광개시제의 농도를 달리하면서 이에 따른 내수압을 측정하여 이를 다음 표 4에 나타내었다. By varying the concentration of the photoinitiator for 100 g of the urethane acrylate composition of Example 1, the resulting water pressure was measured and shown in Table 4 below.
[표 4][Table 4]
(mmH2O)Water pressure
(mmH 2 O)
비교예Comparative example 1: One: 투습방수제Breathable waterproofing agent 제조 Produce
상기 실시예 1에서 우레탄 아크릴레이트 조성물 대신 제조예 1에서 제조된 화합물만을 사용하여 투습방수제를 제조하였다.Instead of the urethane acrylate composition in Example 1 using only the compound prepared in Preparation Example 1 to prepare a moisture-permeable waterproofing agent.
내수압과 투습성을 상기 실시예 1과 같은 방법으로 측정한 결과, 다음 표 5에 나타내었다.As a result of measuring the water pressure and moisture permeability in the same manner as in Example 1, it is shown in Table 5 below.
비교예Comparative example 2: 2: 투습방수제Breathable waterproofing agent 제조 Produce
상기 실시예 1에서 우레탄 아크릴레이트 조성물 대신 제조예 2에서 제조된 화합물만을 사용하여 투습방수제를 제조하였다.Instead of the urethane acrylate composition in Example 1 to prepare a moisture-permeable waterproofing agent using only the compound prepared in Preparation Example 2.
내수압과 투습성을 상기 실시예 1과 같은 방법으로 측정한 결과, 다음 표 5에 나타내었다.As a result of measuring the water pressure and moisture permeability in the same manner as in Example 1, it is shown in Table 5 below.
비교예Comparative example 3: 3: 투습방수제Breathable waterproofing agent 제조 Produce
상기 실시예 1에서 우레탄 아크릴레이트 조성물 대신 제조예 1에서 제조된 화합물와 제조예 2에서 제조된 화합물이 95 : 5의 중량비로 혼합한 우레탄 아크릴레이트 조성물을 사용하여 투습방수제를 제조하였다.Instead of the urethane acrylate composition in Example 1, the moisture-permeable waterproofing agent was prepared using the urethane acrylate composition in which the compound prepared in Preparation Example 1 and the compound prepared in Preparation Example 2 were mixed at a weight ratio of 95: 5.
내수압과 투습성을 상기 실시예 1과 같은 방법으로 측정한 결과, 다음 표 5에 나타내었다.As a result of measuring the water pressure and moisture permeability in the same manner as in Example 1, it is shown in Table 5 below.
[표 5]TABLE 5
(mmH2O)Water pressure
(mmH 2 O)
g/m2 24 hr Breathable
g / m 2 24 hr
도 1은 화학식 1a의 화합물에 대한 FT-IR이다.1 is an FT-IR for a compound of Formula 1a.
도 2는 화학식 2a의 화합물에 대한 FT-IR이다.2 is FT-IR for the compound of Formula 2a.
도 3은 투습방수제 처리 전의 섬유의 SEM 사진이다.3 is a SEM photograph of the fiber before the water vapor barrier agent treatment.
도 4는 본 발명에 따른 투습방수제로 코팅한 섬유의 SEM 사진이다.Figure 4 is a SEM photograph of the fiber coated with a moisture-permeable waterproofing agent according to the present invention.
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| US5200463A (en) * | 1991-04-04 | 1993-04-06 | Huels, Ag | Aqueous, radiation-curable urethane acrylate emulsions and process for producing the same |
| KR100506142B1 (en) | 1997-12-31 | 2005-09-26 | 주식회사 케이씨씨 | Binary Polyurethane Composition |
| JP2000119970A (en) | 1998-10-15 | 2000-04-25 | Teijin Ltd | Moisture permeable waterproof fabric |
| KR20080098109A (en) * | 2007-05-04 | 2008-11-07 | (주) 큐리프 | Synthetic method of (meth)acryl terminated polyurethane and uv curable waterproofing adhesive using the synthetic polyurethane for electronic device protection |
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