CN105051271A - Spandex fiber having excellent chlorine resistance and discoloration resistance and method for preparing same - Google Patents
Spandex fiber having excellent chlorine resistance and discoloration resistance and method for preparing same Download PDFInfo
- Publication number
- CN105051271A CN105051271A CN201380056187.0A CN201380056187A CN105051271A CN 105051271 A CN105051271 A CN 105051271A CN 201380056187 A CN201380056187 A CN 201380056187A CN 105051271 A CN105051271 A CN 105051271A
- Authority
- CN
- China
- Prior art keywords
- resistant
- chlorine
- discoloration
- resistance
- spandex fibre
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000000460 chlorine Substances 0.000 title claims abstract description 74
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 74
- 239000000835 fiber Substances 0.000 title claims abstract description 64
- 229920002334 Spandex Polymers 0.000 title claims abstract description 60
- 239000004759 spandex Substances 0.000 title claims abstract description 60
- 238000002845 discoloration Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 12
- 239000004814 polyurethane Substances 0.000 claims abstract description 11
- 229920002635 polyurethane Polymers 0.000 claims abstract description 11
- 238000009987 spinning Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000006259 organic additive Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 6
- 238000000578 dry spinning Methods 0.000 claims abstract description 5
- 239000002516 radical scavenger Substances 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims description 37
- -1 bis--tert-butyl-hydroxy phenyl Chemical group 0.000 claims description 16
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical class NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 150000003673 urethanes Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 229940123457 Free radical scavenger Drugs 0.000 claims description 4
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 3
- ZRHAQPGGMXXARO-UHFFFAOYSA-N 1,1-diamino-3,3-dimethylurea Chemical compound CN(C(=O)N(N)N)C ZRHAQPGGMXXARO-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 17
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004804 winding Methods 0.000 abstract description 2
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 14
- 229910001701 hydrotalcite Inorganic materials 0.000 description 9
- 229960001545 hydrotalcite Drugs 0.000 description 9
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 8
- 239000001095 magnesium carbonate Substances 0.000 description 7
- 235000014380 magnesium carbonate Nutrition 0.000 description 7
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- 239000012209 synthetic fiber Substances 0.000 description 4
- CXUJOBCFZQGUGO-UHFFFAOYSA-F calcium trimagnesium tetracarbonate Chemical compound [Mg++].[Mg++].[Mg++].[Ca++].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O CXUJOBCFZQGUGO-UHFFFAOYSA-F 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910000515 huntite Inorganic materials 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 230000009182 swimming Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RRYNADVPFHNWDZ-UHFFFAOYSA-N S(=O)(=O)=NC(=O)N.NNC(NN)=O Chemical compound S(=O)(=O)=NC(=O)N.NNC(NN)=O RRYNADVPFHNWDZ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
-
- 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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The purpose of the present invention is to solve problems of easy discoloration of a chlorine-resistant spandex fiber employing an inorganic chlorine resistant agent when left in the air, a short-term or temporary chlorine resistant effect, and the loss of a unique trait of a spandex fiber, and to provide a spandex fiber having excellent chlorine resistance and discoloration resistance and a method for preparing the same, wherein the spandex fiber is prepared by adding and mixing, as organic additives for improving chlorine resistance added in the preparation of a normal chlorine-resistant spandex fiber, at least one compound among symmetric di-hindered hydroxyphenyl-based compounds and mono-hindered hydroxyphenyl-based compounds, an additive containing a semicarbazide-based compound having heat resistance and a radical scavenger function, and an urethane-based additive containing a tertiary butyl group serving as a secondary antioxidant, into a slurry of a polyurethane solution, thereby preparing a spinning solution, followed by defoamation, dry spinning, and winding.
Description
Technical field
The present invention relates to spandex (spandex) fiber and manufacture method thereof with good chlorine resistance and discoloration-resistant.Especially, the present invention relates to while improving chlorine resistance, the spandex fibre that can prevent the discoloration-resistant of Yellowing and the physical property damage caused by the multiple environmental factor of periphery from improving and manufacture method thereof, described spandex fibre, except the inorganic chlorine-resistant agent added for giving chlorine resistance, obtains by being added with organic additive in addition.
Background technology
Spandex fibre refers to the synthetic fiber made with polyurethane fiber and elastic yarn, nylon compared to prior art or polyster fibre, belongs to high added value fiber.Spandex fibre, because having the features such as easy stretching, lightweight, good toughness, is widely used in the making of the sportswear such as women underwear or swimming suit or silk stocking, child's paper diaper.Therefore, spandex fibre not only receives the concern of international fiber manufacturing company, and domestic many synthetic fiber manufacturers also show keen interest to this.But synthetic fiber aspect at home, than other synthetic fiber, the manufacturing technology level of spandex fibre is slightly inferior to foreign country in spinning and post processing, therefore, needing the research by continuing to guarantee basic technology, developing the elastic yarn production technology of high-quality.
But, the large shortcoming of spandex fibre is low heat resistance and chlorine resistance, and relevant technical problem estimates the large obstacle that will become elastomer market development of being obstructed, therefore, if this problem can be solved, then great contribution is made in the development for elastic yarn and elastomer market.
For catering to this type of market demand characteristic, people actively develop the research being intended to develop chlorine fastness spandex fibers.Generally speaking, if spandex fibre and active chlorine are (such as, carry out chlorination swimming pool and for washing and the chlorine class bleaching agent of processing technology) Long contact time, then because there is the decomposition of fibrous strands, reduce the elasticity of the feature/advantage as spandex fibre.Therefore, chlorine fastness spandex fibers be for opposing chlorine component to the damage of fiber, maintain the product that the intrinsic retractility of spandex fibre develops, especially there is the life-span maintaining swimming suit and the indispensable proterties maintained needed for retractility.
In the prior art, what most chlorine fastness spandex fibers was paid close attention in essence is use inorganic chlorine-resistant agent, and such as hydrotalcite, basic magnesite and basic magnesite and huntite mixed mineral maintain chlorine resistance.But when spandex fibre is exposed in the multiple environmental factors of periphery such as such as ultraviolet, heat and air smog, generation xanthochromia and physical property sustain damage, or because being placed on air, NO
xgas, UV line, waste gas is medium easily tends to variable color.
As mentioned above, use chlorine-resistant agent to improve chlorine resistance to spandex fibre, but continuation being restricted, and has within very short time or the tendency of volatilizing instantaneously, especially when using chlorine-resistant agent, being difficult to the inherent characteristic guaranteeing spandex fibre.Sometimes being added with organic additive in addition for maintaining the continuation of chlorine resistance, although this is to improving the continuation effectiveness to some extent of chlorine resistance, still there is restriction to improving discolouration.In addition, according to the processing conditions of the fabric of use spandex fibre, there is the problem that cannot play effect because of coming off of organic additive.
The spandex fibre of prior art lays stress on to be given on chlorine resistance, but the present invention is by adding NO in addition
xgas and daylight show the diaminourea sulfonylurea with heat resistance and free radical scavenger function of superperformance and play the compound comprising the tert-butyl group of secondary antioxidants effect and mix, product compared to prior art, discolouration be improved significantly.Therefore, the present invention can be applicable to fabric processing (such as, front processing and aft-loaded airfoil), long term storage when cannot use because of variable color during chlorine process effectively.
Summary of the invention
Technical problem
The object of the present invention is to provide the spandex fibre and manufacture method thereof with good chlorine resistance and discoloration-resistant, described spandex fibre not only can play chlorine resistance, and the improvement of the duration of this effect, but also discolouration can be improved simultaneously, owned inherent characteristic can be kept thus, thus solve when the chlorine fastness spandex fibers of inorganic for use of the prior art chlorine-resistant agent is exposed to multiple environmental factor or is positioned in air, this fiber is easy to the performance of variable color, and solve the of short duration or phenomenon that occurs instantaneously of chlorine resistance effect and lose the problem of spandex fibre inherent characteristic.
Technological means
The feature with the spandex fibre of good chlorine resistance and discoloration-resistant of the present invention is, in the manufacture process of the chlorine fastness spandex fibers of routine, by adding following material and carry out mixing to manufacture spinning solution in the slurry of polyurethane solutions, after froth breaking, by dry spinning and convolute manufacture: as improve chlorine resistance organic additive be selected from least one compound be obstructed in group that (symmetricallydi-hindered) hydroxy phenyl compound and (mono-hindered) hydroxy phenyl compound that is singly obstructed form by symmetry two, there is diaminourea (disemicarbazide) the class material of heat resistance and free radical scavenger function and play the additive comprising the tert-butyl group of secondary antioxidants effect.
In addition, the invention is characterized in, the spandex fibre manufactured by said method has good chlorine resistance and discoloration-resistant.
Invention effect
Detailed description of the invention
The specific embodiment of the present invention is embodiment 1 to embodiment 6.
Invention embodiment
The manufacture method with the spandex fibre of good chlorine resistance and discoloration-resistant of the present invention comprises: the first step is the step manufacturing polyurethane prepolymer solution, first diphenyl methane-4 is made, 4'-vulcabond and molecular weight be 1800 to 3000 polytetramethylene ether diol react, be manufactured on the polyurethane prepolymer that two ends all have isocyanates, the dimethylacetylamide then adding dissolving manufactures polyurethane prepolymer solution.
Second step is the step being manufactured polyurethane solutions by above-mentioned polyurethane prepolymer solution, by adding the ethylenediamine and diethylamine solution manufacture polyurethane solutions that are dissolved in dimethylacetylamide in described pre-polymer solution.
3rd step is manufacture the step of spinning solution by adding to add in the polymer of polyurethane solutions, and in the step of this manufacture spinning solution, the additive used is photostabilizer, inorganic chlorine-resistant agent and other organic chlorine-resistant agent etc.
In the present invention, photostabilizer comprises titanium dioxide, preferably with the 0.1wt% to 1.0 for the solids content relative to polyurethane solutions polymer
wthe scope of application of t%, particularly preferably 0.3wt% to 0.6wt% adds.
In the present invention, comprise the inorganic chlorine-resistant agent of 0.1wt% to 5.0wt%, described inorganic chlorine-resistant agent is the hydrotalcite represented by following chemical formula 1, the basic magnesite compound represented by following chemical formula 2 or basic magnesite and the huntite represented by following chemical formula 3 and mixed mineral thereof, wherein, hydrotalcite compound is the most applicable.
Chemical formula 1
M
20 xal
m(OH)
y(An
-)
2
In above formula, M
2+for Mg
2+or Zn
2+, the anion of An-to be valence be n, x, y are at least 2 or above integer, and z, m are integer.Above-mentioned An-is OH-, F-, Cl-, Br-, NO
3-, SO
4 2-, CH
3cOO-, CO
3 2-, HPO
4 2-, Fe (CN)
6 3-, oxalate ion and salicylate ion.
According to the present invention, hydrotalcite compound particle is such as Mg
4al
2(OH)
12cO
3h
2o, Mg
4.5al
2(OH)
13cO
33.5H
2o, Mg
6al
2(OH)
16cO
3h
2o, Mg
8al
2(OH)
20cO
3h
2o, Mg
4al
2(OH)
12cO
3h
2o, Mg
4.5al
2(OH)
13cO
3, Mg
6al
2(OH)
16cO
3, Mg
8al
2(OH)
20cO
3, Mg
4al
2(OH)
20cO
3, Mg
4.5al
2(OH)
13(CO
3)
0.6o
0.4, Mg
6al
2(OH)
16(CO
3)
0.7o
0.3, Mg
4.5al
2(OH)
12.2(CO
3)
0.8o
0.6, Mg
4al
2(OH)
12(CO
3)
0.6o
0.4deng, wherein, preferred Mg
4al
2(OH)
12cO
3h
2o.
Chemical formula 2
M
2+ x(An
-)
yM
2+(OH)
z·mH
2O
In above formula, M
2+for Mg
2+or Zn
2+, the anion of An-to be valence be n, x, y are at least 2 or above integer, z and m is integer.Above-mentioned An-is OH-, F-, Cl-, Br-, NO
3-, SO
4 2-, CH
3cOO-, CO
3 2-, HPO
4 2-, Fe (CN)
6 3-, oxalate ion and salicylate ion.
In the present invention, be such as Mg by the compound of the chemical formulation of basic magnesite
4(CO
3)
4mg (OH)
2h
2o, Mg
3(CO
3)
3mg (OH)
23H
2o, Mg
4(CO
3)
4mg (OH)
2, and Mg
3(CO
3)
3mg (OH)
2, MgCO
3deng.
Chemical formula 3
MG
3Ca(CO
3)
3
Preferably, for the hydrotalcite compound that inorganic chlorine-resistant agent of the present invention is through coating, relative to above-mentioned hydrotalcite compound the coating stearic acid of 1wt% to 3wt%, the melamine compounds of 0.5wt% to 2wt%, in the polymer of polyurethane solutions, add the described hydrotalcite of 1wt% to 10wt% and mix.Preferably, above-mentioned melamine compounds choice for use melamine phosphate.
When using the melamine compounds of stearic acid or the 0.5wt% being less than 1wt% respectively, without coating effect.In contrast, when respectively to use more than 3wt% or 10wt%, in coating and effect, there is no large difference, then not preferred because economy is not high.
In addition, manufacture of the present invention there is the spandex fibre of good chlorine resistance and discoloration-resistant time, as the organic additive of the improvement chlorine resistance added in addition in slurry, symmetry two hindered hydroxyphenyl group compounds can be used (such as, four [methylene-2-(3,5-bis--tert-butyl-hydroxy phenyl) propionic ester] methane), single hindered hydroxyphenyl group compounds (such as 1,1,3-tri-(2'-methyl-4'-hydroxyl-5'-tert-butyl-phenyl) butane).And relative to the solids content of polymer, symmetry two hindered hydroxyphenyl group compounds is preferably 0.1wt% to 2.0wt%.Relative to the solids content of polymer, single hindered hydroxyphenyl group compounds is preferably 0.1wt% to 3.0wt%, more preferably 0.5wt% to 1.5wt%.
In addition, manufacture of the present invention there is the spandex fibre of good chlorine resistance and discoloration-resistant time, add the diaminourea compounds with heat resistance and free radical scavenger function further with the amount of 0.5wt% to 3.0wt%, preferably 1.0wt% to 2.0wt% and mix, described diaminourea compounds is such as 1 of hindered amine compound, 1,1', 1'-tetramethyl-4,4'-(methylene-two-p-phenylene) diaminourea or 1,6-hexa-methylene two (N, N-dimethyl diaminourea).
In addition, manufacture of the present invention there is the spandex fibre of good chlorine resistance and discoloration-resistant time, drop into the amount of about 1.0wt% the urethanes additive comprising the tert-butyl group that plays secondary antioxidants effect with about 0.1wt% further and mix, described urethanes additive is the compound that such as tertiarybutyldiethanolamine and 4,4'-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) copolymerization are made.
As mentioned above, in polyurethane solutions, drop into inorganic chlorine-resistant agent and improve the additive, organic additive etc. of its function and carry out mixing to manufacture spinning solution, after froth breaking, carry out spinning by dry-spinning process and reel, can manufacture and of the present invention there is good chlorine resistance and the spandex fibre of discoloration-resistant.
Embodiment
Below, will the present invention will be described in more detail in conjunction with the embodiments, but following embodiment is only for the present invention will be described but not limit.
Embodiment 1
In stream of nitrogen gas, make 518g diphenyl methane-4,4'-vulcabond and 2328g polytetramethylene ether diol (molecular weight is 1800) at 90 DEG C with stirring reaction 95 minutes, be manufactured on the polyurethane prepolymer that two ends have isocyanates thus.After prepolymer is cooled to room temperature, adds 4269g dimethylacetylamide and dissolve, thus obtain polyurethane prepolymer solution.
Then, 43g ethylenediamine and 9.1g diethylamine are dissolved in 1889g dimethylacetylamide, and add above-mentioned pre-polymer solution below 9 DEG C, thus obtain polyurethane solutions.
Relative to the solids content of above-mentioned polymer, adding following material as additive mixes: the titanium dioxide as photostabilizer of 0.1wt%, the 1wt% melamine phosphate, the stearic hydrotalcite [Mg of 2wt% that are coated with for hydrotalcite as chlorine-resistant agent of 4wt%
4al
2(OH)
12cO
33H
2o], and in slurry, add following material further and mix: four [methylene-2-(3 of (di-hindered) hydroxy phenyl compounds that is obstructed as symmetry two of 0.5wt%, 5-bis--tert-butyl-hydroxy phenyl) propionic ester] methane, 1.0wt% as 1 of list hindered hydroxyphenyl group compounds, 1, 3-tri-(2'-methyl-4'-hydroxyl-5'-tert-butyl-phenyl) butane, 1.5wt% as 1 of diaminourea sulfonylurea, 1, 1', 1'-tetramethyl-4, the tertiarybutyldiethanolamine and 4 of 4'-(methylene-two-p-phenylene) diaminourea and 0.5wt%, 4'-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), obtain spinning solution thus.
After froth breaking is carried out to spinning solution, in dry-spinning process, spinning temperature is set to 260 DEG C, reels with the winding speed that 900m/ divides, manufacture the spandex fibre silk of 3 long filament 40 DENIER (3filaments40denier) with this.
Chlorine resistance evaluation is carried out to the above-mentioned spandex fibre silk made, and shows the result in following table 1.
For evaluating the chlorine resistance of the spandex fibre silk of above-mentioned acquisition, by the strength retention in method evaluation chlorine water below.
When by spandex fibre silk stretching 50%, process 1 hour at pH4.5 and in the water of 99-100 DEG C, carry out drying and cooling at normal temperatures, impregnated in active chlorine dose at normal temperatures and be 3.5ppm and pH is in the 80L chlorine water of 7.6 after 120 hours, calculate strength retention by following formula.Be used for evaluating brute force by MEL, specimen length is 10cm, utilizes the unit of 32kgf to measure with the draw speed of 1000mm/min (crosshead speed).
Strength retention (%)=S/S
o× 100
* (S
o: brute force before treatment; S: the brute force after process)
In addition, for evaluating the discoloration-resistant of spandex fibre silk, discolouration (chromatism measurement) difference owing to three kinds of browning factors is measured by method below.
After the spandex fibre precursor of each experimental example becomes the textiles of form of fabric, make the sample of wide 3cm, long 10cm.After each sample is processed 20 minutes in the bath containing 1g/L refining agent, 1g/LNaOH at 80 DEG C, air dry 12 hours.
(1) heat-treat condition: heat treatment 10 minutes in the baking box of 200 DEG C.
(2) UV lamp treatment conditions: place 24 hours under UV-B lamp.
(3) NO
xgas treatment condition: utilize sodium nitrate and phosphoric acid to produce NO
xafter gas, place 24 hours under this identical conditions.
Use the Color-view of BYKGardner company
tMmeasure discoloration, with Yellow value time untreated for b1, the Yellow value after process is b2, and after being calculated by △ b=b2-b1, discolouration difference (aberration) is shown.△ b value is less, represents that Yellowing is lower.
Embodiment 2
Remove in the above-described embodiment 1 using 2.0wt% as 1 of diaminourea compounds, 1,1', 1'-tetramethyl-4, outside 4'-(methylene-two-p-phenylene) diaminourea, use polymers manufacturing spandex fibre silk in the same manner as in Example 1, under the condition identical with above-described embodiment 1, evaluate chlorine resistance and discoloration-resistant, and show the result in table 1.
Embodiment 3
Except interpolation 1, two (the N of 6-hexa-methylene, N-dimethyl diaminourea) as outside the diaminourea compounds in above-described embodiment 1, use polymers manufacturing spandex fibre silk in the same manner as in Example 1, under the condition identical with above-described embodiment 1, evaluate chlorine resistance and discoloration-resistant, and show the result in table 1.
Embodiment 4
Except the tertiarybutyldiethanolamine and 4 used in above-described embodiment 1 of 1.0wt%, outside the polyurethane of 4'-methylene two (cyclohexyl isocyanate), use the polymers manufacturing spandex fibre silk identical with embodiment 1, under the condition identical with above-described embodiment 1, evaluate chlorine resistance and discoloration-resistant, and show the result in table 1.
Embodiment 5
Except use huntite and basic magnesite mixed mineral are as except the inorganic chlorine-resistant agent in above-described embodiment 1, use the polymers manufacturing spandex fibre silk identical with embodiment 1, under the condition identical with above-described embodiment 1, evaluate chlorine resistance and discoloration-resistant, and show the result in table 1.
Embodiment 6
Except use basic magnesite is as except the inorganic chlorine-resistant agent in above-described embodiment 1, uses the polymers manufacturing spandex fibre silk identical with embodiment 1, under the condition identical with above-described embodiment 1, evaluate chlorine resistance and discoloration-resistant, and show the result in table 1.
Comparative example 1
Except the urethane additive not using the diaminourea compounds in above-described embodiment 1 and comprise the tert-butyl group, use the polymers manufacturing spandex fibre silk identical with embodiment 1, under the condition identical with above-described embodiment 1, evaluate chlorine resistance and discoloration-resistant, and show the result in table 1.
Comparative example 2
Except not using the urethanes additive comprising the tert-butyl group in above-described embodiment 1, use the polymers manufacturing spandex fibre silk identical with embodiment 1, under the condition identical with above-described embodiment 1, evaluate chlorine resistance and discoloration-resistant, and show the result in table 1.
Comparative example 3
Except not using the single hindered hydroxyphenyl group compounds in above-described embodiment 1, symmetry two hindered hydroxyphenyl group compounds, diaminourea compounds and comprising the urethanes additive of the tert-butyl group, and only use outside inorganic chlorine-resistant agent, use the polymers manufacturing spandex fibre silk identical with embodiment 1, under the condition identical with above-described embodiment 1, evaluate chlorine resistance and discoloration-resistant, and show the result in table 1.
Table 1: chlorine resistance and discoloration-resistant evaluation result
Above-described embodiment is only in order to illustrate the present invention but not to be limited the present invention, those skilled in the art should be understood that, can modify to the present invention, be out of shape or be equal to and replace and do not depart from the spirit and scope of the present invention, above-mentioned amendment, distortion or equivalent replacement all should be encompassed in right of the present invention.
Industrial applicibility
The present invention has following feature: can obtain and have good chlorine resistance and the spandex fibre of discoloration-resistant.
Claims (5)
1. a manufacture has the method for the spandex fibre of good chlorine resistance and discoloration-resistant, it is characterized in that, in the manufacture process of the chlorine fastness spandex fibers of routine, in the slurry of polyurethane solutions, add following material and carry out mixing to manufacture spinning solution, after froth breaking, by dry spinning and convolute manufacture: comprise symmetry two hindered hydroxyphenyl group compounds and single hindered hydroxyphenyl group compounds as the organic additive improving chlorine resistance, comprise the additive of the diaminourea compounds with heat resistance and free radical scavenger function, and play the urethanes additive comprising the tert-butyl group of secondary antioxidants effect.
2. manufacture according to claim 1 has the method for the spandex fibre of good chlorine resistance and discoloration-resistant, it is characterized in that, as symmetry two hindered hydroxyphenyl group compounds, use four [methylene-2-(3,5-, the bis--tert-butyl-hydroxy phenyl) propionic ester] methane of the 0.1wt% to 2.0wt% for solids content; And as single hindered hydroxyphenyl group compounds, use 1,1 of the 1.0wt% to 3.0wt% for solids content, 3-tri-(2'-methyl-4'-hydroxyl-5'-tert-butyl-phenyl) butane.
3. manufacture according to claim 1 has the method for the spandex fibre of good chlorine resistance and discoloration-resistant, it is characterized in that, as diaminourea compounds, use 0.5wt% to 3.0wt% as 1,1,1' of hindered amine compound, 1'-tetramethyl-4,4'-(methylene-two-p-phenylene) diaminourea or 1,6-hexa-methylene two (N, N-dimethyl diaminourea).
4. manufacture according to claim 1 has the method for the spandex fibre of good chlorine resistance and discoloration-resistant, it is characterized in that, as the described urethanes additive comprising the tert-butyl group playing secondary antioxidants effect, use the compound that the tertiarybutyldiethanolamine of about 0.1wt% to 1.0wt% and 4,4'-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) copolymerization are made.
5. the method manufacture according to any one of claim 1-3 there is good chlorine resistance and the spandex fibre of discoloration-resistant.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2013/011410 WO2015088062A1 (en) | 2013-12-10 | 2013-12-10 | Spandex fiber having excellent chlorine resistance and discoloration resistance and method for preparing same |
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| CN105051271B CN105051271B (en) | 2018-04-17 |
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| JP3090826B2 (en) * | 1993-11-24 | 2000-09-25 | 株式会社クラレ | Polyurethane composition and fiber comprising the same |
| KR101157328B1 (en) * | 2009-12-31 | 2012-06-15 | 주식회사 효성 | Anti-chlorine and anti-discoloration Spandex Fiber and Preparation Method thereof |
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|---|---|
| WO2015088062A1 (en) | 2015-06-18 |
| CN105051271B (en) | 2018-04-17 |
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