KR20150089612A - Polyurethan elastic fiber having improved anti-microbe and anti-discoloration - Google Patents
Polyurethan elastic fiber having improved anti-microbe and anti-discoloration Download PDFInfo
- Publication number
- KR20150089612A KR20150089612A KR1020140010461A KR20140010461A KR20150089612A KR 20150089612 A KR20150089612 A KR 20150089612A KR 1020140010461 A KR1020140010461 A KR 1020140010461A KR 20140010461 A KR20140010461 A KR 20140010461A KR 20150089612 A KR20150089612 A KR 20150089612A
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- KR
- South Korea
- Prior art keywords
- polyurethane
- elastic yarn
- discoloration
- polyurethane elastic
- antimicrobial
- Prior art date
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 37
- 238000002845 discoloration Methods 0.000 title claims abstract description 14
- 210000004177 elastic tissue Anatomy 0.000 title abstract description 5
- 239000004814 polyurethane Substances 0.000 claims abstract description 36
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 4
- 239000004599 antimicrobial Substances 0.000 claims description 13
- 230000000845 anti-microbial effect Effects 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 9
- -1 complex metal oxide Chemical class 0.000 abstract description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 abstract description 2
- 229940088710 antibiotic agent Drugs 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000004383 yellowing Methods 0.000 description 8
- 238000009987 spinning Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 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 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 206010057190 Respiratory tract infections Diseases 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229920003226 polyurethane urea Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000028327 secretion Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 206010017533 Fungal infection Diseases 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
- D06M11/42—Oxides or hydroxides of copper, silver or gold
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/10—Filtering or de-aerating the spinning solution or melt
- D01D1/103—De-aerating
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/32—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/36—Cored or coated yarns or threads
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/441—Yarns or threads with antistatic, conductive or radiation-shielding properties
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/449—Yarns or threads with antibacterial properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
Abstract
Description
본 발명은 항균성과 내변색성이 우수한 폴리우레탄 탄성사에 관한 것이다. 더욱 상세하게는 은(Ag) 이온을 다공성 구조 물질에 담지시킨 항균제로서 칼슘(Ca), 마그네슘(Mg), 알루미늄(Al), 티타늄(Ti), 실리콘(Si) 및 지르코늄(Zr)으로 이루어진 군으로부터 적어도 하나를 선택하여서 된 원소를 포함하는 금속 산화물 또는 복합 금속 산화물로 이루어진 항균제를 함유하는 폴리우레탄 탄성사에 관한 것이다.The present invention relates to a polyurethane elastic yarn excellent in antibacterial properties and discoloration resistance. More particularly, the present invention relates to an antimicrobial agent comprising silver (Ag) ions supported on a porous structural material, which is composed of calcium (Ca), magnesium (Mg), aluminum (Al), titanium (Ti), silicon (Si) and zirconium And an antimicrobial agent composed of a metal oxide or a composite metal oxide containing at least one element selected from the group consisting of the elements.
폴리우레탄 탄성사는 탄성과 탄성 회복력이 우수하여 스타킹이나 여성용 속옷류 및 신축성 직물에 많이 이용되고 있으며, 에어로빅, 수영복으로의 용도도 계속 확대되고 있다.Polyurethane elastic yarn is excellent in elasticity and resilience, and is widely used for stockings, women's underwear, and stretchable fabrics. The use of polyurethane elastic yarns as aerobic and swimwear is also continuously expanding.
그러나, 몸에서 배출되는 여러 가지 분비물에 의하여 의류에 많은 종류의 세균류 및 곰팡이류가 부착 서식하는 경우가 발생하게 되는데, 이 중에는 직물에 부착하여 인체에 해로움을 주지는 않지만 의류를 변질, 착색, 오염시켜 악취를 발생시키는 것도 있고, 직접적으로 인체에 해를 입히는 경우도 있다. 특히 여성의 거들 및 브래이저와 같은 속옷에 탄성사를 사용하는 경우에는 땀 등에 의한 분비물로 인하여 세균 또는 곰팡이류가 탄성사에 서식하는 경우도 발생할 수 있다. However, due to various secretions from the body, many types of fungi and fungi attach to the clothing. In this case, it is not harmful to the human body by attaching to the cloth, but the clothes are deteriorated, It may cause bad odor and may directly harm the human body. In particular, when elastic fibers are used for underwear such as female girdles and braziers, bacterial or fungal infections may occur due to secretion by sweat or the like.
이를 해결하기 위하여, 한국 등록특허 제445313호에서는 항균제로서 ZnO, SiO2, 알칼리금속산화물 등으로 구성되는 유리 금속 화합물을 사용하여 항균성을 탄성사에 부여하고, 탄성사 제조과정 중 200℃ 이상의 고온의 방사 공정 중 탄성사의 황변은 일어나지 않으나, 상기 항균제는 탄성사 제조시 사용되는 폴리우레탄용 용매인 디메틸아세트아미드 또는 디메틸포름아마이드와 같은 극성 용매에서 잘 응집된다. 그 결과 방사 공정에서 방출 압력 상승과 사절이 많이 발생하여 장기간에 걸쳐 항균성 섬유의 안정된 방사가 어려운 문제가 발생하였다. 그리고 탄성사 고분자인 폴리우레탄에 투입하기 전, 밀링 또는 샌드 그라인딩 공정을 거쳐야 하는데 폴리우레탄에 투입하기에 적합한 항균제의 2차 응집 크기인 15㎛ 이하를 얻기 위해서는 장시간, 과도한 밀링 공정이 필요하며, 이 과정 중에 항균제가 회색으로 변색됨으로 인해 최종 항균성 탄성사 색상이 회색을 띄는 문제가 발생하였다.In order to solve this problem, Korean Patent Registration No. 445313 discloses a method of imparting antimicrobial activity to elastic fibers by using a free metal compound composed of ZnO, SiO 2 , and alkali metal oxide as an antimicrobial agent, The yellowing of the middle elastic yarn does not occur, but the antibacterial agent is agglomerated well in a polar solvent such as dimethylacetamide or dimethylformamide, which is a polyurethane solvent used in the production of elastic yarn. As a result, the increase of the discharge pressure and the increase of the yarn tension in the spinning process resulted in a problem that the stable spinning of the antibacterial fiber was difficult over a long period of time. In order to obtain a secondary aggregation size of 15 .mu.m or less suitable for the polyurethane, it is necessary to perform an excessive milling process for a long period of time, and the milling or sand grinding process is required before the polyurethane The color of the final antibacterial elastic yarn became gray due to discoloration of the antimicrobial agent to gray.
또한, 한국 특허공개 제2002-0095604호에서는 0.1 ~ 2중량%의 은과 20 ~ 50중량%의 아연이 담지된 무기 세라믹을 폴리우레탄우레아 탄성사 전체 중량에 대하여 0.2 ~ 2중량%를 첨가하는 방법을 개시하고 있다. 그러나, 상기 방법은 아연의 함유량이 20 ~ 50중량%로서 상당히 많아 환경 오염 및 신체 유해성 문제를 야기시킬 수 있으며, 또한 은 제올라이트화합물의 입자 사이즈가 2㎛ 정도로서 방사시 조업성이 저하되는 문제가 있었다. Korean Patent Laid-Open Publication No. 2002-0095604 discloses a method of adding 0.2 to 2% by weight of inorganic ceramics containing 0.1 to 2% by weight of silver and 20 to 50% by weight of zinc to the total weight of the polyurethane-urea elastic yarn Lt; / RTI > However, the above method has a problem that the content of zinc is 20 to 50% by weight, which may cause environmental pollution and physical harmfulness, and that the silver zeolite compound has a particle size of about 2 탆, .
한국 등록특허 제163496호, 한국 공개특허 제1995-18734호, 한국 공개특허 제2000-27866호 및 한국 공개특허 제2000-59821호에서는 은과 지르코늄 금속 이온이 2~60중량%가 함유된 무기 세라믹 또는 4중량%의 은이 담지된 무기 세라믹을 항균제로 폴리우레탄우레아 탄성사에 첨가하는 방법을 개시하고 있다. 그러나, 상기 방법들은 무기세라믹 내의 은 담지량이 2중량% 이상이기 때문에 UV, 대기 스모그 및 자외선에 장시간 노출시 은이 변색(갈변)되어 이를 포함하는 제품도 쉽게 갈변하여 외관의 품위를 잃게 되는 문제가 발생되며, 고가의 은 가격에 의하여 제조 비용이 상승하게 되는 문제가 있었다. Korean Patent No. 163496, Korean Patent Publication No. 1995-18734, Korean Patent Publication No. 2000-27866 and Korean Patent Publication No. 2000-59821 disclose an inorganic ceramic containing 2 to 60% by weight of silver and zirconium metal ion Or 4% by weight of silver-supported inorganic ceramics is added to the polyurethane-urea elastic yarn as an antimicrobial agent. However, since the amount of silver supported in inorganic ceramics is 2% by weight or more, the above methods cause discoloration (browning) of silver when exposed to UV, atmospheric smog and ultraviolet rays for a long time, And the manufacturing cost is increased due to the high price of silver.
또한, 일본특허공개 평7-166425호에서는 항균제로서 나노 은을 사용하여 항균성을 부여하고 있는데 나노 은의 입자 크기를 1-100nm로 한정하고 있다. 그러나, 1-100nm의 나노 은은 그 색상이 회색이므로 폴리우레탄에 혼합하여 방사할 경우 원사의 색상을 황색 및 회색으로 변색시키는 문제점이 발생하고 있었다. Japanese Patent Laid-Open Publication No. Hei 7-166425 discloses that nano silver is used as an antimicrobial agent to impart antibacterial properties, but the particle size of nano silver is limited to 1-100 nm. However, since the nano silver of 1-100 nm is gray in color, there arises a problem of discoloring the yarn color to yellow and gray when it is mixed with polyurethane.
이에 본 발명은 종래의 이와 같은 문제점을 해결하기 위한 것으로 방사 공정을 거쳐도 황변의 문제를 일으키지 않으며, 내변색성과 반영구적으로 항균성을 부여한 폴리우레탄 탄성사를 제공하는데 그 목적이 있다.Accordingly, it is an object of the present invention to provide a polyurethane elastic yarn which does not cause a problem of yellowing even after a spinning process and imparts discoloration resistance and semi-permanent antibacterial property to the conventional problems.
본 발명에 따른 항균성 및 내변색성이 우수한 폴리우레탄 탄성사는 은(Ag) 이온을 다공성 구조 물질에 담지시킨 항균제로서 칼슘(Ca), 마그네슘(Mg), 알루미늄(Al), 티타늄(Ti), 실리콘(Si) 및 지르코늄(Zr)으로 이루어진 군으로부터 적어도 하나의 원소를 선택하여서 되는 금속 산화물 또는 복합 산화물로 이루어진 항균제를 함유하는 것을 특징으로 한다.The polyurethane elastic yarn excellent in antimicrobial and discoloration resistance according to the present invention is an antibacterial agent having silver (Ag) ions carried on a porous structural material and contains calcium (Ca), magnesium (Mg), aluminum (Al), titanium And at least one element selected from the group consisting of silicon (Si) and zirconium (Zr).
본 발명에 따른 항균성 및 내변색성이 우수한 폴리우레탄 탄성사는 폴리우레탄 중합물에 대한 적절한 분산을 위해서 상기 항균제의 입도가 2㎛ 이하, 바람직하게 1㎛ 이하의 크기를 가지는 것을 특징으로 한다. The polyurethane elastic yarn excellent in antimicrobial and discoloration resistance according to the present invention is characterized in that the particle size of the antibacterial agent is 2 mu m or less, preferably 1 mu m or less, for proper dispersion of the polyurethane polymer.
본 발명에 따른 항균성 및 내변색성이 우수한 폴리우레탄 탄성사는 상기 항균제의 함량을 폴리우레탄 고형분에 대해 0.1 ~ 5.0중량%, 바람직하게는 0.1 ~ 3.0중량%로 하는 것을 특징으로 한다. The polyurethane elastic yarn excellent in antimicrobial and discoloration resistance according to the present invention is characterized in that the content of the antibacterial agent is 0.1 to 5.0% by weight, preferably 0.1 to 3.0% by weight, based on the polyurethane solid content.
본 발명의 폴리우레탄 탄성사는 방사 공정을 거쳐도 황변의 문제를 일으키지 않으며, 그 결과 내변색성과 반영구적으로 항균성이 우수한 효과가 있다.The polyurethane elastic yarn of the present invention has no yellowing problem even after the spinning process, and as a result, it has an excellent discoloration resistance and an excellent antimicrobial effect semi-permanently.
이와 같은 본 발명을 다음에서 상세하게 설명하기로 한다. Hereinafter, the present invention will be described in detail.
본 발명의 탄성사는 바람직하게 폴리우레탄 탄성사이다.The elastic yarn of the present invention is preferably a polyurethane elastic yarn.
본 발명에서의 탄성사 제조시에 사용되는 세그먼트 폴리우레탄 중합체는 당 분야에서 이미 공지되어 있는 바와 같이 유기디이소시아네이트 및 고분자 디올을 반응시켜 폴리우레탄 전구체를 제조한 후, 이를 유기 용매에 용해시킨 후 디아민과 모노아민과 반응시킴으로써 얻어진다. As is well known in the art, the segment polyurethane polymer used in the production of elastic yarn in the present invention may be produced by reacting an organic diisocyanate and a polymer diol to prepare a polyurethane precursor, dissolving the polyurethane precursor in an organic solvent, Monoamine. ≪ / RTI >
본 발명에서 사용되는 유기 디이소시아네이트는 디페닐메탄-4,4'-디이소시아네이트, 헥사메틸렌디이소시아네이트, 톨루엔디이소시아네이트, 부틸렌디이소시아네이트, 수소화된 4,4'-디페닐메탄디이소시아네이트 등을 예로 들 수 있고, 상기 고분자 디올로는 폴리테트라메틸렌에테르 글리콜, 폴리프로필렌글리콜, 폴리카보네이트디올 등을 예로 들 수 있다. 또한 상기 디아민류는 쇄연장제로서, 그 구체적인 예로는 에틸렌디아민, 프로필렌디아민, 하이드라진 등이 있다. 한편, 상기 모노아민은 쇄종지제로서, 구 구체적인 예로는 디에틸아민, 모노에탄올아민, 디메틸아민 등이 있다. The organic diisocyanate used in the present invention is exemplified by diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate and the like Examples of the polymeric diol include polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, and the like. Further, the diamines are chain extenders, and specific examples thereof include ethylenediamine, propylenediamine, hydrazine and the like. On the other hand, the monoamine is a chain terminator, and specific examples thereof include diethylamine, monoethanolamine, dimethylamine, and the like.
그 밖에 기타 첨가제로서는 UV 안정제, 산화방지제, Nox 가스 황변 방지제, 염착 증진제, 내염소제, 소광제 및 항균제 등이 부가적으로 사용될 수 있다. As other additives, UV stabilizer, antioxidant, No x gas yellowing inhibitor, adhesion promoter, chlorine remover, quencher and antimicrobial agent may be additionally used.
본 발명에 의하면, 상기 항균제로는 은(Ag) 이온을 다공성 구조 물질에 담지시킨 항균제로서 칼슘(Ca), 마그네슘(Mg), 알루미늄(Al), 티타늄(Ti), 실리콘(Si) 및 지르코늄(Zr)으로 이루어진 군으로부터 적어도 하나의 원소를 선택하여서 되는 금속 산화물 또는 복합 산화물로 이루어진 것을 함유할 수 있다.According to the present invention, the antimicrobial agent includes calcium (Ca), magnesium (Mg), aluminum (Al), titanium (Ti), silicon (Si) and zirconium Zr) selected from the group consisting of a metal oxide or a composite oxide.
이와 같은 항균제는 폴리우레탄 중합물에 대한 적절한 분산 또는 우수한 분산을 위해서 입도를 2㎛ 이하, 바람직하게 1㎛ 이하로 설정하는 것이 좋으며, 상기 항균제의 함량은 폴리우레탄 고형분에 대해 0.1 ~ 5.0중량%, 바람직하게는 0.1 ~ 3.0중량%로 하는 것을 좋다.Such an antibacterial agent is preferably set to a particle size of 2 탆 or less, preferably 1 탆 or less, for proper dispersion or excellent dispersion of the polyurethane polymer. The content of the antibacterial agent is preferably 0.1 to 5.0% by weight based on the polyurethane solid content By weight is 0.1 to 3.0% by weight.
본 발명에서 사용하는 항균제는 다른 첨가제와 함께 혼합하여 폴리우레탄 중합체 용액에 첨가할 수도 있고, 다른 첨가제를 먼저 첨가한 후 방사 직전에 첨가할 수 있고, 그 반대의 경우도 가능하다. The antimicrobial agent used in the present invention may be added to the polyurethane polymer solution by mixing with other additives, or may be added immediately before the addition of the other additives and vice versa.
이하 본 발명을 실시예에 의거하여 더욱 상세히 설명하면 다음과 같으며, 이들 실시예는 단지 분 발명을 보다 명확하게 이해시키기 위한 것으로 본 발명의 범위를 한정하고자 하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the scope of the present invention in order to more clearly understand the present invention.
실시예Example
폴리우레탄 중합체에 은(Ag)을 칼슘-인산염(평균입도 0.5 ㎛)에 담지된 항균제로 원사내 함량이 1.5중량%가 되도록 투입하였다. 이어서 통상의 산화 방지제, 황변 방지제, 내염소제, 소광제를 투입하고, 그라인더 밀로 밀링을 분산액을 제조하였다. 이 분산액을 폴리우레탄 중합체 용액에 소정량 첨가하여 방사 원액을 제조하였다. 이 방사원액을 탈포시킨 후, 건식방사 공정에서 40데니아 탄성사를 제조하였다.The polyurethane polymer was loaded with an antimicrobial agent containing silver (Ag) in a calcium phosphate (average particle size of 0.5 mu m) so that the content in the yarn was 1.5 wt%. Subsequently, a conventional antioxidant, a yellowing inhibitor, a chlorine-containing agent and a quencher were added and milled by a grinder mill to prepare a dispersion. A predetermined amount of this dispersion was added to the polyurethane polymer solution to prepare a spinning solution. After the spinning liquid was defoamed, a 40 denier elastic yarn was produced in a dry spinning process.
비교예Comparative Example
항균제로서 종래 기술에서 설명한 한국 특허공개 제1995-18734호의 실시예 1에 개시된 은 3.8중량%와 지르코늄 35중량%가 첨가제 된 비다공성 무기계 항균 세라믹을 사용하는 것을 제외하고는 실시예와 동일하게 실시하여 탄성사를 제조하였다.Porous inorganic antibacterial ceramics added with 3.8% by weight of silver and 35% by weight of zirconium as disclosed in Example 1 of Korean Patent Laid-open Publication No. 1995-18734 described in the prior art as antibacterial agent were used in the same manner as in Example Elastic yarn was produced.
상기 실시예와 비교예에서 제조한 폴리우레탄 탄성사에 대한 항균성과 내벽색성을 다음과 같은 방법으로 평가하고 그 결과는 다음 표 1과 같다. The antibacterial properties and inner wall coloring of the polyurethane elastic yarns prepared in the above Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Table 1 below.
(1) 항균성 평가(1) Evaluation of antimicrobial activity
폴리우레탄 탄성사의 환편물 시료를 이용하여 다음과 같은 방법으로 항균성을 평가하였다. 황색포도상 구균(ATCC6538, Staphylococcus aureus)과 폐렴쌍 구균(ATCC4352 Steptcoccus pneumonia)을 시험균으로 채택하여 한국산업규격 K 0693 -2001 방법으로 항균성(정균감소율)을 평가하였다.Antimicrobial activity was evaluated by the following method using a circular knitted fabric of polyurethane elastic yarn. Staphylococcus aureus (ATCC6538, Staphylococcus aureus ) and pneumococcus (ATCC4352 Steptcoccus pneumonia ) was used as a test organism and antibacterial activity (bacteriostatic reduction rate) was evaluated by Korean Industrial Standard K 0693 -2001.
항균성(정균감소율)(%) = [(대조편의 18시간 배양 후 생균수 - 시험편의 18시간 배양 후 생균수)/대조편의 18시간 배양 후 생균수]×100(Number of viable cells after incubation for 18 hours on the control piece-number of viable cells after 18 hours of culture of the test piece) / number of viable cells after 18 hours of culture on the control piece] × 100
- 시험편: 탄성사 환편물- Test specimen:
- 대조편: 면(한국산업규격 K 0905-1996에 해당되는 면)- Reference: Cotton (Cotton corresponding to Korean Industrial Standard K 0905-1996)
(2) 내변색성 평가(2) Evaluation of discoloration resistance
내열성 시험Heat resistance test
공기순환이 가능한 건조오븐에서 시료를 200℃에서 10분 동안 처리하였다. 시료를 처리하기 전후에, 칼라-뷰(Color-view)(가든너(Gardener), 미국)로 시료의 “b”값(황변값)을 각각 측정하였다. 시료 처리 후 b값과 처리전 b값의 차이를 Δb로 표시하였다.The samples were treated in a drying oven capable of air circulation at 200 ° C for 10 minutes. Before and after the sample was treated, the "b" value (yellowing value) of the sample was measured with a Color-view (Gardener, USA). The difference between b value after treatment and b value before treatment is indicated by Δb.
NOxNOx 가스 시험 Gas test
NOx가스에 대한 내성을 평가하기 위해, 이온교환수 300mmL, 85% 인산수용액 6mL, 질산 나트륨(NaNO3) (10g/L) 40mL의 혼합 용액으로 NOx 가스 발생액을 제조하고, 밀폐된 용기 내에 상기 용액을 넣고 시료를 이 용기 내에서 상온, 24시간 동안 NOx 가스로 처리하였다. In order to evaluate the resistance to NOx gas, a NOx gas generating solution was prepared from a mixed solution of 300 mm L of ion exchange water, 6 mL of an 85% phosphoric acid aqueous solution and 40 mL of sodium nitrate (NaNO 3 ) (10 g / L) And the sample was treated with NOx gas in the vessel at room temperature for 24 hours.
시료를 처리하기 전후에, 칼라-뷰(Color-view)(가든너(Gardener), 미국)로 시료의 “b”값(황변값)을 각각 측정하였다. 시료 처리 후 b값과 처리전 b값의 차이를 Δb로 표시하였다.Before and after the sample was treated, the "b" value (yellowing value) of the sample was measured with a Color-view (Gardener, USA). The difference between b value after treatment and b value before treatment is indicated by Δb.
UVUV 시험 exam
UV 시험은 UV-B 램프를 사용하였다. UV-B램프下 온도는 37℃ 수준으로 24시간 처리하였다. For the UV test, a UV-B lamp was used. UV-B lamp temperature was maintained at 37 ℃ for 24 hours.
시료를 처리하기 전후에, 칼라-뷰(Color-view)(가든너(Gardener), 미국)로 시료의 “b”값(황변값)을 각각 측정하였다. 시료 처리 후 b값과 처리전 b값의 차이를 Δb로 표시하였다.Before and after the sample was treated, the "b" value (yellowing value) of the sample was measured with a Color-view (Gardener, USA). The difference between b value after treatment and b value before treatment is indicated by Δb.
상기 표1에 의하면, 본 발명에 따른 폴리우레탄 탄성사(실시예)의 경우 황색포도상구균 및 폐렴쌍구균 감소율이 99.8 ~ 99.9%로서 한국 특허공개 제1995-18734호(비교예)의 경우에 비해서 상당히 우수하다는 것을 알 수 있으며, 내변색성도 우수하다는 것을 알 수 있다.
According to the above Table 1, in the case of the polyurethane elastic yarn (Examples) according to the present invention, the reduction ratio of Staphylococcus aureus and pneumococcus is 99.8 to 99.9%, which is considerably superior to that of Korean Patent Laid-Open Publication No. 1995-18734 And it is also found that the discoloration resistance is also excellent.
Claims (5)
The polyurethane elastic yarn according to claim 1, wherein the content of the antibacterial agent is 0.1 to 3.0% by weight based on the polyurethane solid content.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484874A (en) * | 2018-03-23 | 2018-09-04 | 惠州市远安新材料有限公司 | A kind of polyurethane material, high-elastic Antibacterial polyurethane class powder puff and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07157957A (en) * | 1993-10-14 | 1995-06-20 | Kanebo Ltd | Production of antimicrobial nonwoven fabric comprising polyurethane elastic filament |
| JPH07166425A (en) * | 1993-11-24 | 1995-06-27 | Asahi Chem Ind Co Ltd | Polyurethane elastic fiber |
| JP2006028453A (en) * | 2004-07-21 | 2006-02-02 | Nisshinbo Ind Inc | Polyurethane elastomer and elastic fiber |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07157957A (en) * | 1993-10-14 | 1995-06-20 | Kanebo Ltd | Production of antimicrobial nonwoven fabric comprising polyurethane elastic filament |
| JPH07166425A (en) * | 1993-11-24 | 1995-06-27 | Asahi Chem Ind Co Ltd | Polyurethane elastic fiber |
| JP2006028453A (en) * | 2004-07-21 | 2006-02-02 | Nisshinbo Ind Inc | Polyurethane elastomer and elastic fiber |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484874A (en) * | 2018-03-23 | 2018-09-04 | 惠州市远安新材料有限公司 | A kind of polyurethane material, high-elastic Antibacterial polyurethane class powder puff and preparation method thereof |
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