KR20030010205A - Dye Additive Composition for Improving Dyeability of Polyurethane Fiber and Synthetic Leather and Method of Preparing the Same - Google Patents
Dye Additive Composition for Improving Dyeability of Polyurethane Fiber and Synthetic Leather and Method of Preparing the Same Download PDFInfo
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- KR20030010205A KR20030010205A KR1020010045049A KR20010045049A KR20030010205A KR 20030010205 A KR20030010205 A KR 20030010205A KR 1020010045049 A KR1020010045049 A KR 1020010045049A KR 20010045049 A KR20010045049 A KR 20010045049A KR 20030010205 A KR20030010205 A KR 20030010205A
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- diisocyanate
- glycol
- additive composition
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- polyurethane
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- 239000000654 additive Substances 0.000 title claims abstract description 49
- 230000000996 additive effect Effects 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims description 8
- 239000002649 leather substitute Substances 0.000 title description 11
- 229920006306 polyurethane fiber Polymers 0.000 title description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 40
- 239000004814 polyurethane Substances 0.000 claims abstract description 39
- 229920002635 polyurethane Polymers 0.000 claims abstract description 39
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 21
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940113088 dimethylacetamide Drugs 0.000 claims abstract description 11
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 claims abstract description 10
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims abstract description 9
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims abstract description 8
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims abstract description 8
- XKQMKMVTDKYWOX-UHFFFAOYSA-N 1-[2-hydroxypropyl(methyl)amino]propan-2-ol Chemical compound CC(O)CN(C)CC(C)O XKQMKMVTDKYWOX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims abstract description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 claims abstract description 7
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 claims abstract description 7
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims abstract description 7
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims abstract description 4
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 claims abstract description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- SZBXTBGNJLZMHB-UHFFFAOYSA-N 1-chloro-2,4-diisocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1N=C=O SZBXTBGNJLZMHB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 150000001412 amines Chemical class 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- 239000012948 isocyanate Substances 0.000 abstract description 3
- 150000002513 isocyanates Chemical class 0.000 abstract description 3
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 238000004043 dyeing Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 229920005749 polyurethane resin Polymers 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- -1 and thus Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 239000012963 UV stabilizer Substances 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- XJRAOMZCVTUHFI-UHFFFAOYSA-N isocyanic acid;methane Chemical compound C.N=C=O.N=C=O XJRAOMZCVTUHFI-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5285—Polyurethanes; Polyurea; Polyguanides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
본 발명에 따른 폴리우레탄 첨가제 조성물은 단독 이소시아네이트보다 혼합된 이소시아네이트를 활용해서 폴리올과 중합시 여러 가지 효과를 거둘 수 있다는 것이 그 요약이므로, 이소포론 디이소시아네이트(IPDI), 파라페닐렌 디이소시아네이트(PPDI), 1,5-나프탈렌 디이소시아네이트(NDI), 메타페닐렌 디이소시아네이트 (MPDI), 1-클로로-2,4-페닐렌 디이소시아네이트, 톨루엔 디이소시아네이트(TDI), 메틸렌 디이소시아네이트(MDI), 3,3-디메틸디페닐-4,4-디이소시아네이트 및 디아니시딘 디이소시아네이트(DADI)로 이루어진 군으로부터 선택된 제1 디이소시아네이트, 헥사메틸렌 디이소시아네이트(HDI), 2,2,4-트리메틸 헥사메틸렌 디이소시아네이트, 메타테트라메틸 자일렌 디이소시아네이트(TMXDI), 디메틸 디이소시아네이트 (DDI), 4,4-디페닐 메탄 디이소시아네이트(H12MDI) 및 메틸 사이클로헥실 디이소시아네이트로 이루어진 군으로부터 선택된 제2 디이소시아네이트, n-메틸디에탄올아민(MDEA), n-부틸디에탄올아민(BDEA), n-t-부틸디에탄올아민(TBDEA), n-메틸디프로판올아민(MDPA) 및 n-메틸디이소프로판올아민(MDIPA)으로 이루어진 군으로부터 선택된 아민, 및 프로필렌 글리콜(PG), 디프로필렌 글리콜(DPG), 폴리프로필렌 글리콜(PPG), 에틸렌 글리콜(EG), 디에틸렌 글리콜(DEG), 트리에틸렌 글리콜(TEG) 및 폴리에틸렌 글리콜(PEG)로 이루어진 군으로부터 선택된 글리콜을 디메틸 아세트아마이드(DMAC) 또는 디메틸포룸아마이드(DMF) 용매 내에서 중합하여 얻어진다.Since the polyurethane additive composition according to the present invention can summarize various effects of polymerization with polyols by using mixed isocyanates rather than single isocyanates, isophorone diisocyanate (IPDI) and paraphenylene diisocyanate (PPDI) , 1,5-naphthalene diisocyanate (NDI), metaphenylene diisocyanate (MPDI), 1-chloro-2,4-phenylene diisocyanate, toluene diisocyanate (TDI), methylene diisocyanate (MDI), 3, First diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethyl hexamethylene diisocyanate selected from the group consisting of 3-dimethyldiphenyl-4,4-diisocyanate and dianisidine diisocyanate (DADI) , Metatetramethyl xylene diisocyanate (TMXDI), dimethyl diisocyanate (DDI), 4,4-diphenyl methane diisocyanate ( H12MDI) and a second diisocyanate selected from the group consisting of methyl cyclohexyl diisocyanate, n-methyl diethanolamine (MDEA), n-butyl diethanolamine (BDEA), nt-butyl diethanolamine (TBDEA), n- Amines selected from the group consisting of methyldipropanolamine (MDPA) and n-methyldiisopropanolamine (MDIPA), and propylene glycol (PG), dipropylene glycol (DPG), polypropylene glycol (PPG), ethylene glycol (EG) Obtained by polymerizing a glycol selected from the group consisting of diethylene glycol (DEG), triethylene glycol (TEG) and polyethylene glycol (PEG) in a dimethyl acetamide (DMAC) or dimethyl formumamide (DMF) solvent.
Description
발명의 분야Field of invention
본 발명은 폴리우레탄 섬유 및 합성피혁의 염색성을 포함한 기타 물성을 향상시킬 수 있는 염색첨가제 조성물에 관한 것이다. 보다 구체적으로, 본 발명은 용매내에서 2 종의 디이소시아네이트계 화합물, 아민 및 글리콜을 중합시켜 이루어진 중합조성물로서, 폴리우레탄 섬유 및 합성피혁의 염색성을 포함한 기타 물성을 향상시킬 수 있는 염색첨가제 조성물에 관한 것이다. 또한 본 발명은 상기 염색첨가제 조성물을 제조하기 위한 방법도 포함한다.The present invention relates to a dye additive composition capable of improving the physical properties of polyurethane fibers and other physical properties, including dyeing of synthetic leather. More specifically, the present invention is a polymerization composition formed by polymerizing two kinds of diisocyanate compounds, amines and glycols in a solvent, and to a dye additive composition which can improve other properties including dyeing properties of polyurethane fibers and synthetic leather. It is about. The present invention also includes a method for preparing the dye additive composition.
발명의 배경Background of the Invention
폴리우레탄은 파지력(고무의 1.8배), 인열강도(고무의 2배), 파열강도, 탄성등이 월등히 우수하여 주로 합성피혁이나 여성용 파운데이션 및 수영복, 체조복 등의 소재로 활용되고 있다.Polyurethane has excellent grip strength (1.8 times rubber), tear strength (double rubber), burst strength and elasticity, and is mainly used for synthetic leather, women's foundation, swimwear and gym clothes.
그런데, 이와 같이 합성피혁, 스판덱스 등의 원료로 다양하게 사용되고 있는 폴리우레탄은 염색성이 좋지 못하고, 나일론이나 폴리에스터 등의 섬유에 비해서 열 또는 빛(자외선)에 의해 쉽게 열화되며 공기중의 산화 질소(NOx)에 의해 쉽게 변색되는 결점이 있다.However, polyurethane, which is widely used as a raw material such as synthetic leather and spandex, is poor in dyeability, and is easily deteriorated by heat or light (ultraviolet rays) as compared to fibers such as nylon or polyester, and thus, nitrogen oxides in the air ( NO x ) is easily discolored.
이에 따라, 폴리우레탄 섬유 및 합성피혁의 염색성을 향상시킬 목적으로 여러 가지 염색첨가제가 개발되어 사용되고 있지만, 염색 견뢰도 또는 다른 첨가제와의 상용성(compatibility)이 저하되어 제품의 품질과 관련하여 많은 문제를 야기시켜 왔다. 뿐만 아니라, 산화방지를 목적으로 첨가되는 산화방지제나 HALS(hindered amine light stabilizer)와 같은 UV 안정제와의 상용성이 나쁘기 때문에 이들 문제를 해결하기 위한 많은 연구가 진행되어 왔다.As a result, various dyeing additives have been developed and used for the purpose of improving the dyeing properties of polyurethane fibers and synthetic leather. However, dyeing fastness or compatibility with other additives is lowered, which leads to many problems related to product quality. It has caused. In addition, many studies have been conducted to solve these problems because of poor compatibility with UV stabilizers such as antioxidants or HALS (hindered amine light stabilizer) added for the purpose of antioxidant.
미국특허 제2,999,839호에서는 분자량 280 이상의 메타크릴레이트 폴리머를 사용하여 자외선과 연소 가스에 안정적인 폴리우레탄 첨가제를 개시하고 있으나, 염소표백에 의한 섬유의 견뢰도 및 염색성의 저하를 극복할 수 없었다.U.S. Patent No. 2,999,839 discloses a polyurethane additive that is stable to ultraviolet rays and combustion gases by using a methacrylate polymer having a molecular weight of 280 or more, but it is not possible to overcome the degradation of the fastness and dyeability of fibers due to chlorine bleaching.
영국특허 제1,104,127호에서는 상기 미국특허의 문제점을 극복하기 위하여 힌더드 메타크릴레이트를 사용하였지만, 마찬가지로 섬유의 견뢰도 및 염색성의 저하는 해결할 수 없었다.In British Patent No. 1,104,127, hindered methacrylate was used to overcome the problems of the above-mentioned US patent, but likewise, the degradation of the fastness and dyeability of the fiber could not be solved.
본 발명자는 폴리우레탄 섬유 및 합성피혁의 염색첨가제가 갖는 결점을 극복하기 위하여 디이소시아네이트계 화합물과 N-치환 에탄올아민을 중합시켜 제조된 조성물을 사용함으로써, 폴리우레탄의 염색성을 향상시키고, 염색제품의 염색 견뢰도가 우수하며, 산화방지제 및 UV안정제 등의 첨가제와 상용성이 뛰어나 산화방지효과뿐만 아니라 UV, NOx및 열에 대한 안정성이 동반 상승되는 첨가제 조성물을 개발하여 우리나라 특허출원 제2001-35126호(2001. 6. 20출원)로서 특허출원을 하였다. 본 발명은 상기 특허출원의 발명을 더 개량한 것으로, 상기 특허출원 발명이 갖는 장점 외에도 폴리우레탄 레진을 안정화시켜 반응속도를 일정하게 하며, 반응의 안정화로 인하여 품질이 균일한 레진을 생산할 수 있고, 중합반응시 발열반응으로 인한 온도의 조절이 용이하여 점도가 안정화된 레진을 제조할 수 있다.The present inventors use a composition prepared by polymerizing a diisocyanate compound and N-substituted ethanolamine in order to overcome the drawbacks of the dye additive of polyurethane fibers and synthetic leather, thereby improving the dyeability of polyurethane, It is excellent in color fastness, and has excellent compatibility with additives such as antioxidant and UV stabilizer, so as to develop an additive composition that increases not only antioxidant effect but also stability against UV, NO x and heat, and Korea Patent Application No. 2001-35126 ( Patent application on June 20, 2001). The present invention is a further improvement of the invention of the patent application, in addition to the advantages of the patent application invention to stabilize the polyurethane resin to maintain a constant reaction rate, due to the stabilization of the reaction can produce a resin of uniform quality, It is easy to control the temperature due to the exothermic reaction during the polymerization reaction can be prepared a resin stabilized viscosity.
본 발명의 목적은 폴리우레탄 섬유 및 합성피혁의 염색성을 향상시킬 수 있는 염색첨가제 중합조성물을 제공하기 위한 것이다.An object of the present invention is to provide a dye additive polymerization composition that can improve the dyeing properties of polyurethane fibers and synthetic leather.
본 발명의 다른 목적은 폴리우레탄 섬유 및 합성피혁 제품의 염색 견뢰도를 향상시킬 수 있는 염색첨가제 중합조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a dye additive polymerization composition which can improve the dyeing fastness of polyurethane fibers and synthetic leather products.
본 발명의 또 다른 목적은 산화방지 및 UV, NOx및 열에 대한 안정성을 보완하기 위하여 첨가되는 첨가제와 폴리우레탄과의 상용성이 양호한 염색첨가제 중합조성물을 제공하기 위한 것이다.It is still another object of the present invention to provide a dye additive polymerization composition having good compatibility with polyurethane and additives added to prevent oxidation and stability against UV, NO x and heat.
본 발명의 또 다른 목적은 액상으로 되어 있어 용해성이 좋아 사용하기에 간편한 염색첨가제 중합조성물을 제공하기 위한 것이다.Still another object of the present invention is to provide a dye additive polymerization composition which is easy to use because it is in a liquid state and has good solubility.
본 발명의 또 다른 목적은 상기 폴리우레탄의 염색첨가제 중합조성물을 제조하기 위한 방법을 제공하기 위한 것이다.Another object of the present invention is to provide a method for producing a dye additive polymerization composition of the polyurethane.
본 발명의 또 다른 목적은 폴리우레탄 레진을 안정화시켜 반응속도를 일정하게 하며, 반응의 안정화로 인하여 품질이 균일한 폴리우레탄 레진을 생산할 수 있는 첨가제 조성물을 제공하기 위한 것이다.Still another object of the present invention is to provide an additive composition capable of producing a polyurethane resin with a uniform quality due to stabilization of the polyurethane resin to stabilize the reaction rate and stabilization of the reaction.
본 발명의 또 다른 목적은 폴리우레탄 중합반응의 안정화로 인하여 품질이 균일한 폴리우레탄 레진을 생산할 수 있는 첨가제 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide an additive composition capable of producing a polyurethane resin of uniform quality due to the stabilization of the polyurethane polymerization.
본 발명의 또 다른 목적은 폴리우레탄 중합반응시 발열반응으로 인한 온도의 조절이 용이하여 점도가 안정화된 폴리우레탄 레진을 제조할 수 있는 첨가제 조성물을 제공하기 위한 것이다.Still another object of the present invention is to provide an additive composition which can prepare a polyurethane resin having a stabilized viscosity by easily controlling a temperature due to an exothermic reaction during a polyurethane polymerization reaction.
본 발명의 상기 및 기타의 목적들은 모두 하기 설명되는 본 발명에 의해서 모두 달성될 수 있다. 이하 본 발명의 내용을 하기에 상세히 설명한다.The above and other objects of the present invention can all be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.
발명의 요약Summary of the Invention
본 발명에 따른 폴리우레탄 첨가제 조성물은 이소포론 디이소시아네이트 (IPDI), 파라페닐렌 디이소시아네이트(PPDI), 1,5-나프탈렌 디이소시아네이트 (NDI), 메타페닐렌 디이소시아네이트(MPDI), 1-클로로-2,4-페닐렌 디이소시아네이트, 톨루엔 디이소시아네이트(TDI), 메틸렌 디이소시아네이트(MDI), 3,3-디메틸디페닐-4,4-디이소시아네이트 및 디아니시딘 디이소시아네이트(DADI)로 이루어진 군으로부터 선택된 제1 디이소시아네이트, 헥사메틸렌 디이소시아네이트(HDI), 2,2,4-트리메틸 헥사메틸렌 디이소시아네이트, 메타테트라메틸 자일렌 디이소시아네이트(TMXDI), 디메틸 디이소시아네이트(DDI), 4,4-디페닐 메탄 디이소시아네이트(H12MDI) 및 메틸 사이클로헥실 디이소시아네이트로 이루어진 군으로부터 선택된 제2 디이소시아네이트, n-메틸디에탄올아민(MDEA), n-부틸디에탄올아민(BDEA), n-t-부틸디에탄올아민(TBDEA), n-메틸디프로판올아민(MDPA) 및 n-메틸디이소프로판올아민(MDIPA)으로 이루어진 군으로부터 선택된 아민, 및 프로필렌 글리콜(PG), 디프로필렌 글리콜(DPG), 폴리프로필렌 글리콜(PPG), 에틸렌 글리콜(EG), 디에틸렌 글리콜(DEG), 트리에틸렌 글리콜(TEG) 및 폴리에틸렌 글리콜(PEG)로 이루어진 군으로부터 선택된 글리콜을 디메틸 아세트아마이드(DMAC) 또는 디메틸포룸아마이드(DMF) 용매내에서 중합하여 얻어진다.The polyurethane additive compositions according to the invention are isophorone diisocyanate (IPDI), paraphenylene diisocyanate (PPDI), 1,5-naphthalene diisocyanate (NDI), metaphenylene diisocyanate (MPDI), 1-chloro- From the group consisting of 2,4-phenylene diisocyanate, toluene diisocyanate (TDI), methylene diisocyanate (MDI), 3,3-dimethyldiphenyl-4,4-diisocyanate and dianisidine diisocyanate (DADI) Selected first diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethyl hexamethylene diisocyanate, metatetramethyl xylene diisocyanate (TMXDI), dimethyl diisocyanate (DDI), 4,4-diphenyl Second diisocyanate, n-methyldiethanolamine (MDEA), n-butyl selected from the group consisting of methane diisocyanate (H12MDI) and methyl cyclohexyl diisocyanate Amines selected from the group consisting of ethanolamine (BDEA), nt-butyldiethanolamine (TBDEA), n-methyldipropanolamine (MDPA) and n-methyldiisopropanolamine (MDIPA), and propylene glycol (PG), di Glycol selected from the group consisting of propylene glycol (DPG), polypropylene glycol (PPG), ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG) and polyethylene glycol (PEG) is dimethyl acetamide (DMAC). Or dimethylformumamide (DMF) in a solvent.
발명의 구체예에 대한 상세한 설명Detailed Description of the Invention
본 발명에 따른 폴리우레탄 첨가제 조성물은 제1 디이소시아네이트, 제2 디이소시아네이트, 아민 및 글리콜을 용매내에서 중합하여 제조한다. 2 종류의 디이소시아네이트를 사용하면 1종류의 디이소시아네이트를 사용하는 것보다 반응속도, 호환성, 가격 등을 서로 보완할 수 있다. 따라서 2 종류의 디이소시아네이트를 사용하면 보다 우수한 품질의 폴리우레탄 첨가제 조성물을 제조할 수 있다.The polyurethane additive composition according to the invention is prepared by polymerizing a first diisocyanate, a second diisocyanate, an amine and a glycol in a solvent. When two kinds of diisocyanate are used, reaction speed, compatibility, price, etc. can be complemented with each other than using one type of diisocyanate. Therefore, the use of two types of diisocyanate makes it possible to produce polyurethane additive compositions of better quality.
본 발명의 폴리우레탄 첨가제 조성물은 제1 디이소시아네이트 10∼30중량%, 제2 디이소시아네이트 1∼25 중량%, 아민 10∼40 중량%, 글리콜 1∼20 중량% 및 용매 20∼80 중량%로 이루어진다.The polyurethane additive composition of the present invention consists of 10 to 30% by weight of the first diisocyanate, 1 to 25% by weight of the second diisocyanate, 10 to 40% by weight of the amine, 1 to 20% by weight of the glycol and 20 to 80% by weight of the solvent. .
본 발명에서 사용되는 제1 디이소시아네이트의 예로는 이소포론 디이소시아네이트(IPDI), 파라페닐렌 디이소시아네이트(PPDI), 1,5-나프탈렌 디이소시아네이트(NDI), 메타페닐렌 디이소시아네이트(MPDI), 1-클로로-2,4-페닐렌 디이소시아네이트, 톨루엔 디이소시아네이트(TDI), 메틸렌 디이소시아네이트(MDI), 3,3-디메틸디페닐-4,4-디이소시아네이트 및 디아니시딘 디이소시아네이트(DADI) 등이 있으며, 제2 디이소시아네이트의 예로는 헥사메틸렌 디이소시아네이트(HDI), 2,2,4-트리메틸 헥사메틸렌 디이소시아네이트, 메타테트라메틸 자일렌 디이소시아네이트(TMXDI), 디메틸 디이소시아네이트(DDI), 4,4-디페닐 메탄 디이소시아네이트(H12MDI) 및 메틸 사이클로헥실 디이소시아네이트 등이 있다.Examples of the first diisocyanate used in the present invention include isophorone diisocyanate (IPDI), paraphenylene diisocyanate (PPDI), 1,5-naphthalene diisocyanate (NDI), metaphenylene diisocyanate (MPDI), 1 -Chloro-2,4-phenylene diisocyanate, toluene diisocyanate (TDI), methylene diisocyanate (MDI), 3,3-dimethyldiphenyl-4,4-diisocyanate and dianisidine diisocyanate (DADI), etc. Examples of the second diisocyanate include hexamethylene diisocyanate (HDI), 2,2,4-trimethyl hexamethylene diisocyanate, metatetramethyl xylene diisocyanate (TMXDI), dimethyl diisocyanate (DDI), 4, 4-diphenyl methane diisocyanate (H12MDI) and methyl cyclohexyl diisocyanate.
본 발명의 폴리우레탄 첨가제 조성물을 제조하기 위해서는 아민과 글리콜이 더 사용된다. 본 발명에서 사용되는 아민은 그 말단에 히드록실기(-OH)를 함유하는 것으로, 대표적인 것으로 n-메틸디에탄올아민(MDEA), n-부틸디에탄올아민(BDEA), n-t-부틸디에탄올아민(TBDEA), n-메틸디프로판올아민(MDPA), n-메틸디이소프로판올아민(MDIPA) 등이 있다. 아민의 말단에 존재하는 히드록실기는 디이소시아네이트의 -NCO-와 우레탄 반응 또는 우레아 반응을 한다. 따라서 이 경우에는 아민의 말단에 존재하는 히드록실기가 소멸된다. 아민의 히드록실기가 소멸되면, 폴리우레탄 수지에 첨가될 경우, 폴리우레탄 고분자내에 존재하는 -NCO-를 완전하게 반응시키지 못한다. 따라서 본 발명에서는 폴리우레탄 고분자 내에 존재하는 -NCO-를 완전하게 반응시키기 위하여 글리콜을 추가하여 사용한다. 글리콜을 추가하면 히드록실기가 공급되며, 이 공급된 히드록실기는 폴리우레탄 중합시에 폴리우레탄 고분자의 -NCO-와 완전히 반응하여 폴리우레탄의 염색성 및 기타 물성을 개선하게 된다. 본 발명에서 사용되는 글리콜의 예로는 프로필렌 글리콜(PG), 디프로필렌 글리콜(DPG), 폴리프로필렌 글리콜(PPG), 에틸렌 글리콜(EG), 디에틸렌 글리콜(DEG), 트리에틸렌 글리콜(TEG) 및 폴리에틸렌 글리콜(PEG) 등이 있다.To prepare the polyurethane additive composition of the present invention, amines and glycols are further used. The amine used in the present invention contains a hydroxyl group (-OH) at the terminal thereof, and typical examples thereof include n-methyl diethanolamine (MDEA), n-butyl diethanolamine (BDEA), and nt-butyl diethanolamine. (TBDEA), n-methyldipropanolamine (MDPA), n-methyldiisopropanolamine (MDIPA), and the like. The hydroxyl group present at the terminal of the amine undergoes a urethane or urea reaction with -NCO- of the diisocyanate. In this case, the hydroxyl group present at the terminal of the amine is lost. When the hydroxyl group of the amine is extinguished, when added to the polyurethane resin, it does not completely react with -NCO- present in the polyurethane polymer. Therefore, in the present invention, glycol is added and used to completely react -NCO- present in the polyurethane polymer. When glycol is added, a hydroxyl group is supplied, and the hydroxyl group is fully reacted with -NCO- of the polyurethane polymer during polyurethane polymerization to improve the dyeability and other physical properties of the polyurethane. Examples of glycols used in the present invention include propylene glycol (PG), dipropylene glycol (DPG), polypropylene glycol (PPG), ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG) and polyethylene Glycol (PEG) and the like.
본 발명의 폴리우레탄 첨가제 조성물은 제1 디이소시아네이트, 제2 디이소시아네이트, 아민 및 글리콜을 용매내에서 중합하는데, 사용되는 용매로는 디메틸 아세트아마이드(DMAC), 디메틸포룸아마이드(DMF) 등이 있다.The polyurethane additive composition of the present invention polymerizes the first diisocyanate, the second diisocyanate, the amine and the glycol in a solvent, and examples of the solvent used include dimethyl acetamide (DMAC), dimethyl formumamide (DMF), and the like.
본 발명에 따른 폴리우레탄 첨가제 조성물을 제조하는 방법은 다음과 같다.Method for producing a polyurethane additive composition according to the invention is as follows.
수분이 제거되고 질소가 충진된 반응조에 아민과 글리콜을 투입하고, 40∼70 ℃의 온도로 승온시킨다. 아민은 첨가제 조성물을 제조하는데 소요되는 상당량을 투입하고, 글리콜은 전량중에서 약 40∼60 중량을 투입한다.Amine and glycol are added to a reaction tank filled with nitrogen and the water is removed, and the temperature is raised to a temperature of 40 to 70 ° C. The amine adds a substantial amount to prepare the additive composition, and the glycol adds about 40 to 60 weight in total.
상기 승온된 반응조에 제1 디이소시아네이트와 제2 디이소시아네이트를 투입하고, 50∼80 ℃의 온도에서 30∼90 분간 반응시킨다. 제1 디이소시아네이트는 첨가제 조성물을 제조하는데 소요되는 전량의 약 1/2을 투입하고, 제2 디이소시아네이트는 소요되는 전량의 약 1/2을 투입한다.A 1st diisocyanate and a 2nd diisocyanate are thrown into the said heated reaction tank, and it is made to react for 30 to 90 minutes at the temperature of 50-80 degreeC. The first diisocyanate adds about 1/2 of the total amount required to prepare the additive composition, and the second diisocyanate adds about 1/2 of the total amount required.
상기 반응조에 용매를 투입하고, 50∼70 ℃의 온도에서 10∼50 분간 반응시킨다. 용매는 소요되는 전량의 약 1/3을 부가한다.A solvent is put into the said reaction tank, and it is made to react for 10 to 50 minutes at the temperature of 50-70 degreeC. The solvent adds about one third of the total amount required.
상기 반응조에 다시 용매와 제1 디이소시아네이트를 부가하고, 50∼90 ℃의 온도에서 60∼120 분간 반응시킨다. 용매는 소요되는 전량의 약 1/3을 투입하고, 제1 디이소시아네이트는 소요되는 전량의 약 1/2을 부가한다.The solvent and the first diisocyanate are further added to the reaction tank and allowed to react for 60 to 120 minutes at a temperature of 50 to 90 ° C. The solvent adds about one third of the total required and the first diisocyanate adds about one half of the total required.
상기 반응조에 다시 나머지 용매와 나머지 제2 디이소시아네이트를 투입하고, 50∼90 ℃의 온도에서 2∼7 시간 반응시킨다. 여기서 부가되는 용매는 소요되는 전량중에서 약 1/3에 해당하며, 제2 디이소시아네이트는 소요되는 전량중에서 약 1/2에 해당한다.The remaining solvent and the remaining second diisocyanate are further added to the reactor, and reacted at a temperature of 50 to 90 ° C. for 2 to 7 hours. The solvent added here corresponds to about one third of the total amount required, and the second diisocyanate corresponds to about one half of the total amount required.
상기 반응조에 글리콜을 투입하고, 냉각하여 폴리우레탄 첨가제 조성물을 제조한다. 글리콜은 소요되는 전량중에서 약 60∼40 중량%를 이 단계에서 투입한다. 냉각된 첨가제 조성물은 일정량씩 포장하여 출하한다.Glycol is added to the reactor and cooled to prepare a polyurethane additive composition. About 60-40% by weight of glycol is added at this stage. The cooled additive composition is packaged and shipped in a predetermined amount.
종래의 폴리우레탄 첨가제 조성물은 한 종류의 디이소시아네이트와 아민을 용매내에서 중합시키고, 반응정지제를 이용하여 중합반응을 종료시키는데 반하여, 본 발명에서는 반응정지제를 사용하지 않는다. 따라서 본 발명에서는 작업이 간소화되고, 또한 반응시간이 단축되는 결과를 가져온다.Conventional polyurethane additive compositions polymerize one type of diisocyanate and amine in a solvent and terminate the polymerization reaction using a reaction terminator, whereas the reaction terminator is not used in the present invention. Therefore, in the present invention, the work is simplified and the reaction time is shortened.
본 발명의 폴리우레탄 첨가제 조성물은 폴리우레탄 합성피혁이나 폴리우레탄 탄성사 제조시에 첨가되어 염색성을 향상시키며, UV 및 NOx의 방지제, 산화방지제, -NCO- 안정화제로서의 역할을 하기도 한다.The polyurethane additive composition of the present invention is added at the time of manufacture of polyurethane synthetic leather or polyurethane elastic yarn to improve dyeability, and also serves as an inhibitor of UV and NO x , antioxidant, and -NCO- stabilizer.
폴리우레탄 탄성사를 제조할 때, 우레탄 고분자 내에 -NCO-가 존재하면 공기중의 수분과 반응하여 그 중의 일부가 겔화가 일어나는데, 이 겔화된 부분은 방사공정에서 사절(絲切)의 원인이 된다. 따라서 본 발명에 따른 첨가제 조성물을 사용하면, 우레탄 고분자 내에 존재하는 미반응된 -NCO-를 첨가제 중합체의 말단에 존재하는 -OH기와 반응하게 하기 때문에 겔화로 인한 절사현상을 감소시킬 수 있다.In the production of polyurethane elastic yarns, the presence of -NCO- in the urethane polymer reacts with moisture in the air to cause gelation of some of them, which causes the trimming in the spinning process. Therefore, by using the additive composition according to the present invention, the unreacted -NCO- present in the urethane polymer is allowed to react with the -OH group present at the end of the additive polymer, thereby reducing the cutting effect due to gelation.
본 발명의 첨가제 조성물은 우레탄 고분자로서 폴리우레탄 합성피혁이나 탄성사와 호환작용이 우수하기 때문에 첨가제로 사용될 때 탄성강도를 양호하게 하며 염색 후에 세탁견뢰도를 향상시킬 수 있다.Since the additive composition of the present invention has excellent compatibility with polyurethane synthetic leather or elastic yarn as a urethane polymer, it can improve elastic strength when used as an additive and improve washing fastness after dyeing.
본 발명의 첨가제 조성물은 산화방지제, UV 안정제, NOx방지제 등과 함께 사용될 수 있으며, 이들과 호환성이 있기 때문에 이들의 사용량의 일부대신에 사용할 수 있다.The additive composition of the present invention may be used together with antioxidants, UV stabilizers, NO x inhibitors, and the like, and may be used instead of part of their amount because they are compatible with them.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예Example
폴리우레탄 첨가제 조성물 제조Polyurethane Additives Composition
수분이 제거되고 질소가 충진된 반응기에 MDEA 10 g과 PG 3 g을 넣고 55 ℃의 온도로 승온시켰다. 상기 승온된 반응기에 H12MDI 7 g과 MDI 5 g을 넣고 60 ℃의 온도에서 60 분간 반응시켰다. 상기 반응기에 용매로서 DMAC 20 g과 H12MDI 7 g을 넣고 60 ℃의 온도에서 30 분간 반응시켰다. 상기 반응기에 DMAC 20 g과 H12MDI7 g을 다시 넣고 70 ℃의 온도에서 90 분간 반응시켰다. 상기 반응기에 DMAC 20 g과 MDI 5 g을 다시 넣고 70 ℃의 온도에서 5 시간 반응시켰다. 상기 반응조에 PG를 투입하고 냉각시켜 첨가제 조성물을 제조하였다.10 g of MDEA and 3 g of PG were added to a reactor filled with nitrogen and the water was removed, and the temperature was raised to 55 ° C. In the heated reactor, 7 g of H12MDI and 5 g of MDI were added and reacted at a temperature of 60 ° C. for 60 minutes. 20 g of DMAC and 7 g of H12MDI were added to the reactor as a solvent and reacted at a temperature of 60 ° C. for 30 minutes. 20 g of DMAC and 7 g of H12MDI7 were added back to the reactor and reacted at a temperature of 70 ° C. for 90 minutes. 20 g of DMAC and 5 g of MDI were put back into the reactor and reacted at a temperature of 70 ° C. for 5 hours. PG was added to the reactor and cooled to prepare an additive composition.
시험 샘플 제조Trial sample manufacturer
상기에서 제조된 첨가제 조성물을 각각 0.5 %, 0.3 % 사용하여 폴리우레탄을 제조하고, 제조된 폴리우레탄으로부터 시험용 필름을 제조하였다.Polyurethane was prepared using 0.5% and 0.3% of the additive composition prepared above, and a test film was prepared from the prepared polyurethane.
물성측정Property measurement
상기 두 종류의 시료에 대하여 칼라테스트, 세탁견뢰도, 물견뢰도, 연소가스견뢰도, 내열성시험 등을 측정하였고(시험기관: 한국 원사 직물 시험 연구원), 그 결과를 하기 표에 나타내었다. 하기 표의 각 측정값은 본 발명에 따른 폴리우레탄 첨가제 조성물이 포함되지 않은 폴리우레탄을 기준으로 하여 바탕시험(Blank Test) 한 결과이다.Color test, wash fastness, water fastness, combustion gas fastness, heat resistance test and the like of the two types of samples were measured (testing agency: Korea Yarn Textile Testing Institute), and the results are shown in the following table. Each measured value of the following table is the result of the blank test based on the polyurethane which does not contain the polyurethane additive composition which concerns on this invention.
※ 시험기관: 한국 원사 직물 시험 연구원※ Test Institution: Korea Yarn Textile Testing Institute
상기 표 1에 나타난 것과 같이, 본 발명에 따른 폴리우레탄 첨가제 조성물은 최종 폴리우레탄 제품의 염색성 및 기타 물성을 개선하는 효과가 있는 것임을 알 수 있다.As shown in Table 1, it can be seen that the polyurethane additive composition according to the present invention has the effect of improving the dyeability and other physical properties of the final polyurethane product.
본 발명은 혼합된 이소시아네이트를 사용함으로써 염색성, 염색 견뢰도 등의 물성이 우수하고, 산화방지 및 UV, NOx및 열에 대한 안정성을 보완하기 위하여 첨가되는 첨가제와 상용성이 양호하고, 품질이 균일하며, 점도가 안정화된 폴리우레탄 레진을 제조할 수 있는 액상의 첨가제 조성물을 제공하는 효과를 갖는다.The present invention has excellent physical properties such as dyeability, dyeing fastness, etc. by using the mixed isocyanate, good compatibility with additives added to supplement anti-oxidation and stability against UV, NO x and heat, uniform quality, It has the effect of providing a liquid additive composition capable of producing a viscosity stabilized polyurethane resin.
본 발명의 단순한 변형 내지 변경은 이 분야에 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
Claims (8)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0145400B1 (en) * | 1996-02-29 | 1998-07-15 | 박홍기 | Manufacturing method of polyurethane elastic fiber with excellent dyeing and heat resistance |
| KR19990070131A (en) * | 1998-02-17 | 1999-09-15 | 한형수 | Manufacturing method of polyurethane elastic fiber |
| KR20000052482A (en) * | 1999-01-04 | 2000-08-25 | 포만 제프리 엘 | Multiple repair size redundancy |
| KR20020097347A (en) * | 2001-06-20 | 2002-12-31 | 임대준 | Dye Additive Composition for Improving Dyeability of Polyurethane Fiber and Synthetic Leather and Method of Preparing the Same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0145400B1 (en) * | 1996-02-29 | 1998-07-15 | 박홍기 | Manufacturing method of polyurethane elastic fiber with excellent dyeing and heat resistance |
| KR19990070131A (en) * | 1998-02-17 | 1999-09-15 | 한형수 | Manufacturing method of polyurethane elastic fiber |
| KR20000052482A (en) * | 1999-01-04 | 2000-08-25 | 포만 제프리 엘 | Multiple repair size redundancy |
| KR20020097347A (en) * | 2001-06-20 | 2002-12-31 | 임대준 | Dye Additive Composition for Improving Dyeability of Polyurethane Fiber and Synthetic Leather and Method of Preparing the Same |
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