CA2064606A1 - Uv light stable polyamide fibre - Google Patents
Uv light stable polyamide fibreInfo
- Publication number
- CA2064606A1 CA2064606A1 CA 2064606 CA2064606A CA2064606A1 CA 2064606 A1 CA2064606 A1 CA 2064606A1 CA 2064606 CA2064606 CA 2064606 CA 2064606 A CA2064606 A CA 2064606A CA 2064606 A1 CA2064606 A1 CA 2064606A1
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- Canada
- Prior art keywords
- tert
- butyl
- copper
- bis
- 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.)
- Abandoned
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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
- D06P1/64—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 low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/6426—Heterocyclic compounds
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
ABSTRACT
TITLE
UV LIGHT STABLE POLYAMIDE FIBRE
A polyamide fibre having improved UV light stability containing a W light stabilizing package comprising a heterocyclic polymeric hindered amine, an organic hindered phenolic antioxidant, and a third component selected from the group comprising: a benzotriazole compound; a copper compound; an organic phosphite; and a combination of an organic phosphite and a copper compound.
TITLE
UV LIGHT STABLE POLYAMIDE FIBRE
A polyamide fibre having improved UV light stability containing a W light stabilizing package comprising a heterocyclic polymeric hindered amine, an organic hindered phenolic antioxidant, and a third component selected from the group comprising: a benzotriazole compound; a copper compound; an organic phosphite; and a combination of an organic phosphite and a copper compound.
Description
W LIGHT STABLE POLYAMIDE FIBR~
~ACKGRO~ND OF THE INVE~TION
This invention relates to W light stable polyamide f;bre.
It is known that ~V radiation causPs deterioration of both the appearance and physical properties of polyamide fibre. U.S. patent number 4,191,682 (~iba~Geigy) discloses the use of monomeric piperidine carboxylic acids or salts thereof in combination with other additives to improve the W
stability of synthetic polymers. R.D. 19609 (Ciba-Geigy) discloses the use of a polymeric hindered amine in polyolefin to protect against gamma radiation.
It is desired to provide a polyamide fibre that has improved W light stability.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides polyamide fibre having improved UV light stability, said fibre containing a UV light stabilizing package comprising:
(a) a heterocyclic polymeric hindered amine;
(b) an organic hindered phenolic antioxidant; and (c) a third component selected from the group comprising: a benzotriazole compound; a copper compound; an organic phosphite; and a combination of an organic phosphite and a copper compound.
In still another one of its aspects, the invention provides a dyed polyamide fibre having improved W light stability and dye lightfastness, said fibre comprising a dye coated on the surface thereof and a UV light stabilizing package incorporated therein, said package comprising:
(a) a heterocyclic polymeric hindered amine;
lb) an organic hindered phenolic antioxidant;
(c) a third component selected from the group comprising: an organic phosphite compound; and a combination of an orqanic phosphite and a copper compound.
In the present invention, certain W stabilization packages have been found to possess an improved W
206~06 stabilization effect in polyamide fibre. Certain packages have also been found to provide the additional advantage of imparting dye lightfastness ~o dyes coated on the surface of the fibre.
DESCY~I PI`~ON OF THE PREFER~ED EMBODIMENTS
In a particularly preferred embodiment of the present invention, the third component is a copper compound, which not only improves W stabilization in conjunction with the other components of the package, but also provides thermal stabilization. ~enzotriazole is preferred as a third component in circumstances where polyamide containing copper may be difficult to spin into fibre, or in end uses where the presence of copper compounds in ~he yarn is not desirable.
Benzotriazole is preferably not used when the W stabilization package contains copper, since benzotriazole tends to have a yellowing effect on fibre when copper is present. An organic phosphite may be used as the third component by itself in applications where the use of copper compounds is undesireable or in combination with copper compounds in applications were the use of copper compounds is desired.
The heterocyclic hindered amine is preferably selected from the group comprisingl copolymer formed from dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol; poly~l6-l(1,1,3,3-tetramethylbutyl~ amino~-5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino~
hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)imino~; and poly[(6-morpholino-5-triazine-2,4-diyl)[(2,2,6,6-tetramethyl-4-piperidyl) imino]-hexamethylenel(2,2,6,6-tetramethyl-4-piperidyl) imino]]. The W stabilizer package preferably contains at least 10 weight percent hindered amine and most preferably contains from 25 to 75 weight percent hindered amine, based on the weight of said package.
~ he phenolic antioxidant is preferably selected from the group comprising: hindered monophenols, such as 2,6-di-tert-butyl-4-methylphenol or octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; diphenols, such as 2,2'-methylene bis 206~606 (4-methyl-6-tert-butylphenol) or 2,2-methylene bis (4-ethyl-6-tert-butylphenol) or 4,4'-butylidene bis(6-tert-butyl-3-methylphenol) or N,N'-hexamethylene bis (3,5 di-tert-butyl-4-hydroxy hydrocinnamide) or 2,2'-oxamido bis (ethyl 3~s-di tert-butyl-4-hydroxyhydrocinnamate) ~r bis ~3,3-bis (4-hydroxy-3-tert-butylphenyl) butanoic acid] glycol ester or triethyleneglycol bis ~3-tert-butyl-4-hydroxy-5-methyl-hydrocinnamate); and polyphenols such as tetrakis tmethylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane or 1,3,5-trimethyl-2,4,6-tris (3',5'-di-tert-butyl-4'-hydroxybenzyl)-benzene or 3,5-di-tert-butyl-4-hydroxyhydrocinnamic triester with 1,3,5-tris (2-hydroxyethyl)-5-triazine-2,4,6-(lH,3H,5H)-trione or 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-5-triazine 2,4,6-(lH,3H,5H) trione. The W
stabilizer package preferably contains at least 10 weiqht percent phenolic antioxidant and most preferably contains in the range of 25 to 75 weight percent phenolic antioxidant, based on the weight of said package.
The benzotriazole compound is preferably selected from the group comprising: 2(2'-hydroxy-4'-octoxyphenyl)-benzotriazole; 2(2'-hydroxy-5'-t-octylphenyl)-benzotriazole;
~ACKGRO~ND OF THE INVE~TION
This invention relates to W light stable polyamide f;bre.
It is known that ~V radiation causPs deterioration of both the appearance and physical properties of polyamide fibre. U.S. patent number 4,191,682 (~iba~Geigy) discloses the use of monomeric piperidine carboxylic acids or salts thereof in combination with other additives to improve the W
stability of synthetic polymers. R.D. 19609 (Ciba-Geigy) discloses the use of a polymeric hindered amine in polyolefin to protect against gamma radiation.
It is desired to provide a polyamide fibre that has improved W light stability.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides polyamide fibre having improved UV light stability, said fibre containing a UV light stabilizing package comprising:
(a) a heterocyclic polymeric hindered amine;
(b) an organic hindered phenolic antioxidant; and (c) a third component selected from the group comprising: a benzotriazole compound; a copper compound; an organic phosphite; and a combination of an organic phosphite and a copper compound.
In still another one of its aspects, the invention provides a dyed polyamide fibre having improved W light stability and dye lightfastness, said fibre comprising a dye coated on the surface thereof and a UV light stabilizing package incorporated therein, said package comprising:
(a) a heterocyclic polymeric hindered amine;
lb) an organic hindered phenolic antioxidant;
(c) a third component selected from the group comprising: an organic phosphite compound; and a combination of an orqanic phosphite and a copper compound.
In the present invention, certain W stabilization packages have been found to possess an improved W
206~06 stabilization effect in polyamide fibre. Certain packages have also been found to provide the additional advantage of imparting dye lightfastness ~o dyes coated on the surface of the fibre.
DESCY~I PI`~ON OF THE PREFER~ED EMBODIMENTS
In a particularly preferred embodiment of the present invention, the third component is a copper compound, which not only improves W stabilization in conjunction with the other components of the package, but also provides thermal stabilization. ~enzotriazole is preferred as a third component in circumstances where polyamide containing copper may be difficult to spin into fibre, or in end uses where the presence of copper compounds in ~he yarn is not desirable.
Benzotriazole is preferably not used when the W stabilization package contains copper, since benzotriazole tends to have a yellowing effect on fibre when copper is present. An organic phosphite may be used as the third component by itself in applications where the use of copper compounds is undesireable or in combination with copper compounds in applications were the use of copper compounds is desired.
The heterocyclic hindered amine is preferably selected from the group comprisingl copolymer formed from dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol; poly~l6-l(1,1,3,3-tetramethylbutyl~ amino~-5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino~
hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)imino~; and poly[(6-morpholino-5-triazine-2,4-diyl)[(2,2,6,6-tetramethyl-4-piperidyl) imino]-hexamethylenel(2,2,6,6-tetramethyl-4-piperidyl) imino]]. The W stabilizer package preferably contains at least 10 weight percent hindered amine and most preferably contains from 25 to 75 weight percent hindered amine, based on the weight of said package.
~ he phenolic antioxidant is preferably selected from the group comprising: hindered monophenols, such as 2,6-di-tert-butyl-4-methylphenol or octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; diphenols, such as 2,2'-methylene bis 206~606 (4-methyl-6-tert-butylphenol) or 2,2-methylene bis (4-ethyl-6-tert-butylphenol) or 4,4'-butylidene bis(6-tert-butyl-3-methylphenol) or N,N'-hexamethylene bis (3,5 di-tert-butyl-4-hydroxy hydrocinnamide) or 2,2'-oxamido bis (ethyl 3~s-di tert-butyl-4-hydroxyhydrocinnamate) ~r bis ~3,3-bis (4-hydroxy-3-tert-butylphenyl) butanoic acid] glycol ester or triethyleneglycol bis ~3-tert-butyl-4-hydroxy-5-methyl-hydrocinnamate); and polyphenols such as tetrakis tmethylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane or 1,3,5-trimethyl-2,4,6-tris (3',5'-di-tert-butyl-4'-hydroxybenzyl)-benzene or 3,5-di-tert-butyl-4-hydroxyhydrocinnamic triester with 1,3,5-tris (2-hydroxyethyl)-5-triazine-2,4,6-(lH,3H,5H)-trione or 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-5-triazine 2,4,6-(lH,3H,5H) trione. The W
stabilizer package preferably contains at least 10 weiqht percent phenolic antioxidant and most preferably contains in the range of 25 to 75 weight percent phenolic antioxidant, based on the weight of said package.
The benzotriazole compound is preferably selected from the group comprising: 2(2'-hydroxy-4'-octoxyphenyl)-benzotriazole; 2(2'-hydroxy-5'-t-octylphenyl)-benzotriazole;
2(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole;
2(2'-hydroxy-3'5'-di-t-butylphenyl)-benzotriazole; 2(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotr~azole; and 2-(3',5'-bis ~1-methyl-1-phenylethyl)-2'-hydroxyphenyl) benzotriazole. The package preferably contains at least 10 weight percent benzotriazole and most preferably from 25 to 75 weight percent benzotriazole.
The copper compound is preferably selected from copper compounds containing copper cations in either the ~1 or the +2 oxidation state, preferably in the +2 state (i.e. cupric ion).
Copper compounds containing copper cations in the +2 oxidation state that are preferably used include copper acetate, copper bromide, copper iodide or copper nitrate. The package preferably contains at least 20 ppm atomic copper by weight of the fibre and most preferably contains from 40 to 80 ppm atomic copper by weigh~ of the fibre.
206460~
Preferably the W stabilization package having a copper compound as the third component further comprises an organic phosphite compound. This phosphite compound is preferably selected from trivalent phosphorus compounds such as tris (nonylphenyl) phosphite, bis (2,4-di-tert-butyl)-pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite and tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylylenediphosphite. In applications were copper is not desireable as the third component, these phosphite compounds may preferably be used as the third compound. The package preferably contains at least 10 weight percent phosphite and preferably contains no more than 25 weight percent phosphite, since otherwise the polyamide may not be spinnable.
The polyamide fibre is preferably nylon 6,6 fibre.
Nylon 6, nylon 12 or nylon 12,12 may also be used.
The fibre contains at least 0.1~ weight percent W
stabilizer package based on the weight of the fibre and most preferably contains from 0.25 to 1.0 weight percent UV
stabilizer package based on the weight of the fibre.
Preferably, all of the components of the W stabilization package, except for the copper compound, are incorporated into the polyamide by forming a concentrate of them in a polymeric carrier resin, forming the concentrate into pellets, mixing the pellets with polyamide fla~e and melt extruding the mixture of pellets and flake. Fibre is then spun from the melt. Alternatively, if a continuous polymerization process is used to form the polyamide, the W stabilization package may be incorporated into polyamide by extruding the concentrate pellets separately and then injecting the extrudate into an extruder containing molten polyamide. If a batch polymerization process is used to form the polyamide, the W stabilization package may be incorporated into polyamide by adding an aqueous slurry solution containing the W stabilizer additives into an autoclave in which the polyamide is formed by polymerization. Other methods known in the art for incorporating the W stabilization package may be 206~606 used. The method used to combine the W stabilizer additives and polyamide is not essential to the inventlon, provided that the UV additives are evenly dispersed in the polymer before it is spun into filaments. The polymeric carrier is preferably nylon 6 if the package is to be incorporated in nylon 6,6 fibre. The amount of carrier used should be sufficient to facilitate the mixing of polyamide with the stabilizer components in the concentrate.
The copper compound is preferably incorporated into the polymer separately from the other components of the W
stabilization package via addition of an aqueous solution into the autoclave during polyamide formation if a batch polymerization process is used. If a continuous polymerization process is used, an aqueous solution containing the copper compound may be injected into the polymer melt during the pre-polymer stage of the continuous polymerization process. Alternatively, the copper may be incorporated as a concentrate in a carrier resin and added to nylon flake before extrusion and spinning into fibre. The carrier resin for adding copper compound to nylon 6,6 is preferably nylon 6.
The invention will be further described, by way of illustration only, with reference to the following examples.
Fibre samples of 44 dtex, 7 filaments per yarn nylon 6,6 yarn were prepared. All of the samples contained 40 ppm copper, which was incorporated into the polymer by injecting an aqueous copper bromide solution into the nylon melt in a continuous polymerization process. A control sample was prepared that contained copper, but no other stabilizing additives. The other samples had varying amounts of additional additives incorporated into them by extruding a concentrate of the additives in a nylon 6 carrier resin with the nylon 6,6 polymer and then spinning the extrudate. Table 1 gives the abbreviated names of the additives as well as their corresponding trade and chemical names.
~able 2 gives the composition of the additional stabilizing additives incorporated into the polymer fibre for each sample. These samples were exposed to weatherometer conditions using a xenon arc weatherometer, Model Ci35W (Atlas Co., Chicago, Illinois~. Weatherometer exposure was conducted in accordance with ASTM G23-89 (Vol. 07.01). The exposure time to obtain a S0% decrease in both break strength (Test 1) and elongation at break (Test 2) was measured and is reported in Table 2. Exposure time is expressed as ~ilo~oules per square metre. Break strength and elongation at break were both measured using an Instron measuring device.
Table 2 indicates that the exposure time required to obtain a 50% decrease in both break strength and elongation at break was generally longer for the fibres containing either both Irganox 1098 and Chemosorb 944 (Samples 6 and 7), both Irganox 1098 and Tinuvin 622 (Samples 10 and 11), both Irganox 1098 and Irqafos (Sample 12), or a combination of Irganox 1098, Tinuvin 622 and Irgafos (Samples 13 and 14).
Table 1 ABREVIATIOII TRADE ~I~IE Cl/EIIICAI RAltE
Irg 10.8 1~9snox ltl98 lI,NIhexamethylene bis 13,5-di-tert-c~tyl-~ hydro~y-hydror inr,amide) C9-4 Chemosorb 944 Poly tt6 t~l,1,3,3 tetramethylcutyl) aminol-S
trlallne 2,4 diylll~2,2,6,6 tetramethyl ~
pi;xridyll iminol he~amethyltne t2,2,6,6 tetramethyl-4 piperidyl) iminol~
To22 Tinu in 622 ID Copolymer tormed trom dimethyl suecinate and 4 h~lro~y 2,2,6,6 tetramethyl 1-piperidine ethanol ICF Ir9afos 16~ trist2~di~tert butylphenyl) phosphite T234 Tinuvin 234 2-~3 ,5 bis~1 methyl 1-phenylethyll-2 hydroIyphenyll ben20tr~ia201e Co;qxr cuprie bromlde Wl Irgano~ 10.8: -Tlnuvln 622:
Irgatos 166 1:2:1 206~606 ~ble 2 ~POS l T l ON ~UIX~ 7ES7S
~ T6Z2 lCF Test 1 I~2 0.0 0.0 0.0 0.0 189 l77 2 O.S 0.0 0.0 0.0 565 3~1 3 l.0 0.0 0.0 0.0 5~5 0.0 0.5 0.0 0.0 37~ 32 0.~ 1.0 0.0 0.0 619 Ol 6 0.25 0.25 0.0 0.0 750 606 r o.s 0.5 0.0 0.0 950 ~94 0.0 0.0 O.S 0.0 4~1 33 9 0.0 0.0 ~.0 0.0 56B 400 lo 0.25 o.o 0.25 0.0 ~ 19 11 O.S 0.0 0.5 0.0 52 12 0.25 O.o 0.0 0.25 lOS0 ~Sl 13 0.25 0.0 0.5 0.25 902 ~64 1~ 0.16r 0.0 0.~67 0.1~ 700 605 Fibre samples of 110 dtex, 34 filaments per yarn nylon 6,6 yarn were prepared. A control sample was prepared that contained no W stabilizing additives. The other samples had varying amounts of W stabilizinq additives incorporated into them by extruding a concentrate of the additives in a nylon 6 carrier resin with the nylon 6,6 polymer and then spinning the extrudate. None of the samples contained copper.
Table 3 gives the composition of the stabilizing additives incorporated into the polymer fibre for each sample.
(The trade names and chemical names of the abbreviated names used in this table are provided in Table 1). These samples were subjected to UVCON treatment using WCON equipment manufactured by Atlas Co., Chicago, Illinois in accordance with ASTM G23-89 (Vol. 07.01). Break strength was measured at regular intervals using an Instron measuring device. The exposure time, expressed in hours, to obtain a 50~ loss of break strength (Test A) and the hours to break lTest B) were measured. Elongation was measured using an Instron on a regular basis and the hours to 50% loss of elongation (Test C) was measured. These samples were also exposed to weatherometer conditions using a xenon arc weatherometer, Model Ci35W (Atlas Co., Ch~cago, Illinois). Weatherometer 20~606 exposure was conducted in accordance with ASTM G23-89 (Vol.
07.01). Break strength and elongation at break were both measured using an Instron and the exposure time to obtain a 50% decrease in both break strength (Test 1) and elongation at brea~ (Test 2) was measured and is reported in Table 3.
Table 3 indicates that compositions containing a combination of Irganox 1098, Tinuvin 234 and Tinuvin 622 provided improved Test A, Test B, Test C, Test 1 and ~est 2 results over the control sample.
r~sLE3 IHREE CCHPOUEII~ COPPER
COIITA~ C UYLQN ~ARIIS
Sam~le CrOOS;t~ X~ ~
lr~ 1090 ~234 1022 A B S 1 2 COntrOl 0.0 0.0 0.0 r5 2,O 90 185 190 0.007 0.007 0.067 175 540 220 - -2 0.107 0.167 0.167 250 700 325 805 9~0 The samples were exposed to oven ageing at three different temperatures. Oven ageing was conducted in an air convection oven (such as Model Blue M manufactured by General Signals, USA) in accordance with ASTM D776-87 (15.09).
Tensile strength was measured using an Instron and the exposure time to obtain a 50% loss of original tensile strength at three different temperatures is reported in Table 4.
Again Table 4 indicates that compositions containing a combination of Irganox 1098, Tinuvin 234 and Tinuvin 622 provided improved results over the control sample.
TABEE
SUIPle COnPOSIt jOn (X) ~OUr~ tO 50X 105s 0~ Orl9 TerSIle StreMth lrO 10,8 123~ 1o22 110-C 1~0 C loO'C
COntrOI 0.0 0.0 0.0 800 120 25 0.007 0.00~ 0.007 1200 1~0 30 2 O. 16~ O. 10~ O. 16r 1650 2~5 ~2 g Samples of 448 dtex, 68 filaments per yarn nylon 6,6 fibre were prepared. A control sample was prepared that contained no W stabilizing additives and no copper. The other samples had varying amounts of W stabilizing additives and copper incorporated into them by extruding a concentrate of the additives in a nylon 6 carrier resin with the nylon 6,6 polymer and then spinning the extrudate. The fibre samples were subsequently dyed in solution to three different colours, namely mocha, medium granite and amethyst. The dye compositons are provided in Table 5. Table 6 gives the composition of the additives incorporated into the polymer fibre for each sample and reports the results of dye lightfastness tests. The first dye lightfastness test measured the DE (Delta E, the CIE 1976 L*a*b* colour difference formula) of the fibre using a Hunter Lab Tristimulus Colorimeter model D25 m-9, manufactured by Hunter Associates Lab. Inc., Reston, VA in accordance with the Commission Internationale de L'Eclairage (CIE)'s Recommendation on Uniform Color Spaces, Color Difference E~uations, Psychrometric Color Terms, Supplement No.2 to CIE
Publication No. 15, Colorimetry CIE, Paris, 1978, and the second test determined qualitatively the visual appearance of the fibre on a scale of from 1 to 5. As may be seen from this table, fibre containing Irganox 1098, Tinuvin 622, Irgafos 168 (Sample 3) provided improved results. Further improvements were obtained by incorporating copper in addition to these three components (Samples 4 and 5).
Figure 1 gives the results of tenacity retention tests after weatherometer exposure at different levels of exposure.
The lines are mar~ed with numbers corresponding to the sample number provided in Table 6. The weatherometer exposure was conducted in the manner described in Example 1 and tenacity retention was measured with an Ins~ron. Figura 1 shows that a significant improve~ent is obtained with Samples 3 and 5.
20646~
T~BLE 5 ~edium Gr~nlte lltX DYe rrader~rCi'ranet~ ed DYe O.OSDX Irg~lan' ~ello~ 3RL 250X purity 0.087X Irg~lan Blue 3GL 200X purity 0.075X Irg~l n BIDCII RBL 200X purlty 0.030X Irgal~n Rcd BrrAn RL 200X purity t~or,ha 0035X Irgal~n relloll 3RL 250X purity 0.013X Irgalan Red Bro~n RL 200X purity 0.030X IrgDl~n BIac~ RBL 200% purity ~methYs5 0.0033X Irgalrn Yellr,u 3RL 250X purity 0.0160X Irgal~n Rffi Bro~n RL 200X purity 0.0190X Irgalan Blacl~ RBL 200X purlty O.OOBOX Irgalan qluc 3GL 200X purity ~ Irgalan dyes are nanufactured by Clba Ceigy Based on l~elgh~ of dyed fibre DYÇ LlGHTf~STllESS OF U~LOU F13RE~
~OCH~ IIED.GR~RITE AHETN~ST
Colroosition IIJ DE : VISUAI DE : VISU~I DE :VISU~L
Control 250 9.25 ¦ 3 - 8.18 ¦ ~ 7.31 ¦ 2-3 SOO ~4.67 1 1-2 17.67 1 1~2 11.59 1 0 750 1~.16 1 0 21.99 1 0 17.25 1 0 2 Control ~ 250 S.~ ¦ 4-5 5.71 ¦ 4-S 5.70 t 4 50 pSn Cr,ppcr 503 10.80 ¦ 3~4 12.25 1 3 ô.76 t 3-4 750 15.04 1 2 15.92 1 2 12.45 1 2 3 O.SX W1 250 ~.44 1 4-5 3.74 1 ~-5 3.6~ 1 4-S
500 6.36 1 ~ 9.3~ 1 3~4 r-10 14 750 9.62 1 3-~ 12.06 1 3 9.45 1 3~4 4 0.25X W1 ~ 250 2.97 1 ~S 3.70 1 4-S 4.27 1 4-S
50 pprl Cower SOO 6.91 ¦ 4 10.15 ¦ 3 4 6.21 ¦ 4 750 10.57 ¦ 3-4 14.0~ ¦ 2~3 9.43 ¦ 3~4 S O.SX W1 ~ 250 3.26 ¦ 4 5 1.70 I S 2.27 ¦ S
50 i~pm coi~per 500 7.01 1 4 ~.71 1 4 6.19 1 4 750 9.69 j ~ ô.9~ 1 3 ~.99 1 3-4
2(2'-hydroxy-3'5'-di-t-butylphenyl)-benzotriazole; 2(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotr~azole; and 2-(3',5'-bis ~1-methyl-1-phenylethyl)-2'-hydroxyphenyl) benzotriazole. The package preferably contains at least 10 weight percent benzotriazole and most preferably from 25 to 75 weight percent benzotriazole.
The copper compound is preferably selected from copper compounds containing copper cations in either the ~1 or the +2 oxidation state, preferably in the +2 state (i.e. cupric ion).
Copper compounds containing copper cations in the +2 oxidation state that are preferably used include copper acetate, copper bromide, copper iodide or copper nitrate. The package preferably contains at least 20 ppm atomic copper by weight of the fibre and most preferably contains from 40 to 80 ppm atomic copper by weigh~ of the fibre.
206460~
Preferably the W stabilization package having a copper compound as the third component further comprises an organic phosphite compound. This phosphite compound is preferably selected from trivalent phosphorus compounds such as tris (nonylphenyl) phosphite, bis (2,4-di-tert-butyl)-pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite and tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylylenediphosphite. In applications were copper is not desireable as the third component, these phosphite compounds may preferably be used as the third compound. The package preferably contains at least 10 weight percent phosphite and preferably contains no more than 25 weight percent phosphite, since otherwise the polyamide may not be spinnable.
The polyamide fibre is preferably nylon 6,6 fibre.
Nylon 6, nylon 12 or nylon 12,12 may also be used.
The fibre contains at least 0.1~ weight percent W
stabilizer package based on the weight of the fibre and most preferably contains from 0.25 to 1.0 weight percent UV
stabilizer package based on the weight of the fibre.
Preferably, all of the components of the W stabilization package, except for the copper compound, are incorporated into the polyamide by forming a concentrate of them in a polymeric carrier resin, forming the concentrate into pellets, mixing the pellets with polyamide fla~e and melt extruding the mixture of pellets and flake. Fibre is then spun from the melt. Alternatively, if a continuous polymerization process is used to form the polyamide, the W stabilization package may be incorporated into polyamide by extruding the concentrate pellets separately and then injecting the extrudate into an extruder containing molten polyamide. If a batch polymerization process is used to form the polyamide, the W stabilization package may be incorporated into polyamide by adding an aqueous slurry solution containing the W stabilizer additives into an autoclave in which the polyamide is formed by polymerization. Other methods known in the art for incorporating the W stabilization package may be 206~606 used. The method used to combine the W stabilizer additives and polyamide is not essential to the inventlon, provided that the UV additives are evenly dispersed in the polymer before it is spun into filaments. The polymeric carrier is preferably nylon 6 if the package is to be incorporated in nylon 6,6 fibre. The amount of carrier used should be sufficient to facilitate the mixing of polyamide with the stabilizer components in the concentrate.
The copper compound is preferably incorporated into the polymer separately from the other components of the W
stabilization package via addition of an aqueous solution into the autoclave during polyamide formation if a batch polymerization process is used. If a continuous polymerization process is used, an aqueous solution containing the copper compound may be injected into the polymer melt during the pre-polymer stage of the continuous polymerization process. Alternatively, the copper may be incorporated as a concentrate in a carrier resin and added to nylon flake before extrusion and spinning into fibre. The carrier resin for adding copper compound to nylon 6,6 is preferably nylon 6.
The invention will be further described, by way of illustration only, with reference to the following examples.
Fibre samples of 44 dtex, 7 filaments per yarn nylon 6,6 yarn were prepared. All of the samples contained 40 ppm copper, which was incorporated into the polymer by injecting an aqueous copper bromide solution into the nylon melt in a continuous polymerization process. A control sample was prepared that contained copper, but no other stabilizing additives. The other samples had varying amounts of additional additives incorporated into them by extruding a concentrate of the additives in a nylon 6 carrier resin with the nylon 6,6 polymer and then spinning the extrudate. Table 1 gives the abbreviated names of the additives as well as their corresponding trade and chemical names.
~able 2 gives the composition of the additional stabilizing additives incorporated into the polymer fibre for each sample. These samples were exposed to weatherometer conditions using a xenon arc weatherometer, Model Ci35W (Atlas Co., Chicago, Illinois~. Weatherometer exposure was conducted in accordance with ASTM G23-89 (Vol. 07.01). The exposure time to obtain a S0% decrease in both break strength (Test 1) and elongation at break (Test 2) was measured and is reported in Table 2. Exposure time is expressed as ~ilo~oules per square metre. Break strength and elongation at break were both measured using an Instron measuring device.
Table 2 indicates that the exposure time required to obtain a 50% decrease in both break strength and elongation at break was generally longer for the fibres containing either both Irganox 1098 and Chemosorb 944 (Samples 6 and 7), both Irganox 1098 and Tinuvin 622 (Samples 10 and 11), both Irganox 1098 and Irqafos (Sample 12), or a combination of Irganox 1098, Tinuvin 622 and Irgafos (Samples 13 and 14).
Table 1 ABREVIATIOII TRADE ~I~IE Cl/EIIICAI RAltE
Irg 10.8 1~9snox ltl98 lI,NIhexamethylene bis 13,5-di-tert-c~tyl-~ hydro~y-hydror inr,amide) C9-4 Chemosorb 944 Poly tt6 t~l,1,3,3 tetramethylcutyl) aminol-S
trlallne 2,4 diylll~2,2,6,6 tetramethyl ~
pi;xridyll iminol he~amethyltne t2,2,6,6 tetramethyl-4 piperidyl) iminol~
To22 Tinu in 622 ID Copolymer tormed trom dimethyl suecinate and 4 h~lro~y 2,2,6,6 tetramethyl 1-piperidine ethanol ICF Ir9afos 16~ trist2~di~tert butylphenyl) phosphite T234 Tinuvin 234 2-~3 ,5 bis~1 methyl 1-phenylethyll-2 hydroIyphenyll ben20tr~ia201e Co;qxr cuprie bromlde Wl Irgano~ 10.8: -Tlnuvln 622:
Irgatos 166 1:2:1 206~606 ~ble 2 ~POS l T l ON ~UIX~ 7ES7S
~ T6Z2 lCF Test 1 I~2 0.0 0.0 0.0 0.0 189 l77 2 O.S 0.0 0.0 0.0 565 3~1 3 l.0 0.0 0.0 0.0 5~5 0.0 0.5 0.0 0.0 37~ 32 0.~ 1.0 0.0 0.0 619 Ol 6 0.25 0.25 0.0 0.0 750 606 r o.s 0.5 0.0 0.0 950 ~94 0.0 0.0 O.S 0.0 4~1 33 9 0.0 0.0 ~.0 0.0 56B 400 lo 0.25 o.o 0.25 0.0 ~ 19 11 O.S 0.0 0.5 0.0 52 12 0.25 O.o 0.0 0.25 lOS0 ~Sl 13 0.25 0.0 0.5 0.25 902 ~64 1~ 0.16r 0.0 0.~67 0.1~ 700 605 Fibre samples of 110 dtex, 34 filaments per yarn nylon 6,6 yarn were prepared. A control sample was prepared that contained no W stabilizing additives. The other samples had varying amounts of W stabilizinq additives incorporated into them by extruding a concentrate of the additives in a nylon 6 carrier resin with the nylon 6,6 polymer and then spinning the extrudate. None of the samples contained copper.
Table 3 gives the composition of the stabilizing additives incorporated into the polymer fibre for each sample.
(The trade names and chemical names of the abbreviated names used in this table are provided in Table 1). These samples were subjected to UVCON treatment using WCON equipment manufactured by Atlas Co., Chicago, Illinois in accordance with ASTM G23-89 (Vol. 07.01). Break strength was measured at regular intervals using an Instron measuring device. The exposure time, expressed in hours, to obtain a 50~ loss of break strength (Test A) and the hours to break lTest B) were measured. Elongation was measured using an Instron on a regular basis and the hours to 50% loss of elongation (Test C) was measured. These samples were also exposed to weatherometer conditions using a xenon arc weatherometer, Model Ci35W (Atlas Co., Ch~cago, Illinois). Weatherometer 20~606 exposure was conducted in accordance with ASTM G23-89 (Vol.
07.01). Break strength and elongation at break were both measured using an Instron and the exposure time to obtain a 50% decrease in both break strength (Test 1) and elongation at brea~ (Test 2) was measured and is reported in Table 3.
Table 3 indicates that compositions containing a combination of Irganox 1098, Tinuvin 234 and Tinuvin 622 provided improved Test A, Test B, Test C, Test 1 and ~est 2 results over the control sample.
r~sLE3 IHREE CCHPOUEII~ COPPER
COIITA~ C UYLQN ~ARIIS
Sam~le CrOOS;t~ X~ ~
lr~ 1090 ~234 1022 A B S 1 2 COntrOl 0.0 0.0 0.0 r5 2,O 90 185 190 0.007 0.007 0.067 175 540 220 - -2 0.107 0.167 0.167 250 700 325 805 9~0 The samples were exposed to oven ageing at three different temperatures. Oven ageing was conducted in an air convection oven (such as Model Blue M manufactured by General Signals, USA) in accordance with ASTM D776-87 (15.09).
Tensile strength was measured using an Instron and the exposure time to obtain a 50% loss of original tensile strength at three different temperatures is reported in Table 4.
Again Table 4 indicates that compositions containing a combination of Irganox 1098, Tinuvin 234 and Tinuvin 622 provided improved results over the control sample.
TABEE
SUIPle COnPOSIt jOn (X) ~OUr~ tO 50X 105s 0~ Orl9 TerSIle StreMth lrO 10,8 123~ 1o22 110-C 1~0 C loO'C
COntrOI 0.0 0.0 0.0 800 120 25 0.007 0.00~ 0.007 1200 1~0 30 2 O. 16~ O. 10~ O. 16r 1650 2~5 ~2 g Samples of 448 dtex, 68 filaments per yarn nylon 6,6 fibre were prepared. A control sample was prepared that contained no W stabilizing additives and no copper. The other samples had varying amounts of W stabilizing additives and copper incorporated into them by extruding a concentrate of the additives in a nylon 6 carrier resin with the nylon 6,6 polymer and then spinning the extrudate. The fibre samples were subsequently dyed in solution to three different colours, namely mocha, medium granite and amethyst. The dye compositons are provided in Table 5. Table 6 gives the composition of the additives incorporated into the polymer fibre for each sample and reports the results of dye lightfastness tests. The first dye lightfastness test measured the DE (Delta E, the CIE 1976 L*a*b* colour difference formula) of the fibre using a Hunter Lab Tristimulus Colorimeter model D25 m-9, manufactured by Hunter Associates Lab. Inc., Reston, VA in accordance with the Commission Internationale de L'Eclairage (CIE)'s Recommendation on Uniform Color Spaces, Color Difference E~uations, Psychrometric Color Terms, Supplement No.2 to CIE
Publication No. 15, Colorimetry CIE, Paris, 1978, and the second test determined qualitatively the visual appearance of the fibre on a scale of from 1 to 5. As may be seen from this table, fibre containing Irganox 1098, Tinuvin 622, Irgafos 168 (Sample 3) provided improved results. Further improvements were obtained by incorporating copper in addition to these three components (Samples 4 and 5).
Figure 1 gives the results of tenacity retention tests after weatherometer exposure at different levels of exposure.
The lines are mar~ed with numbers corresponding to the sample number provided in Table 6. The weatherometer exposure was conducted in the manner described in Example 1 and tenacity retention was measured with an Ins~ron. Figura 1 shows that a significant improve~ent is obtained with Samples 3 and 5.
20646~
T~BLE 5 ~edium Gr~nlte lltX DYe rrader~rCi'ranet~ ed DYe O.OSDX Irg~lan' ~ello~ 3RL 250X purity 0.087X Irg~lan Blue 3GL 200X purity 0.075X Irg~l n BIDCII RBL 200X purlty 0.030X Irgal~n Rcd BrrAn RL 200X purity t~or,ha 0035X Irgal~n relloll 3RL 250X purity 0.013X Irgalan Red Bro~n RL 200X purity 0.030X IrgDl~n BIac~ RBL 200% purity ~methYs5 0.0033X Irgalrn Yellr,u 3RL 250X purity 0.0160X Irgal~n Rffi Bro~n RL 200X purity 0.0190X Irgalan Blacl~ RBL 200X purlty O.OOBOX Irgalan qluc 3GL 200X purity ~ Irgalan dyes are nanufactured by Clba Ceigy Based on l~elgh~ of dyed fibre DYÇ LlGHTf~STllESS OF U~LOU F13RE~
~OCH~ IIED.GR~RITE AHETN~ST
Colroosition IIJ DE : VISUAI DE : VISU~I DE :VISU~L
Control 250 9.25 ¦ 3 - 8.18 ¦ ~ 7.31 ¦ 2-3 SOO ~4.67 1 1-2 17.67 1 1~2 11.59 1 0 750 1~.16 1 0 21.99 1 0 17.25 1 0 2 Control ~ 250 S.~ ¦ 4-5 5.71 ¦ 4-S 5.70 t 4 50 pSn Cr,ppcr 503 10.80 ¦ 3~4 12.25 1 3 ô.76 t 3-4 750 15.04 1 2 15.92 1 2 12.45 1 2 3 O.SX W1 250 ~.44 1 4-5 3.74 1 ~-5 3.6~ 1 4-S
500 6.36 1 ~ 9.3~ 1 3~4 r-10 14 750 9.62 1 3-~ 12.06 1 3 9.45 1 3~4 4 0.25X W1 ~ 250 2.97 1 ~S 3.70 1 4-S 4.27 1 4-S
50 pprl Cower SOO 6.91 ¦ 4 10.15 ¦ 3 4 6.21 ¦ 4 750 10.57 ¦ 3-4 14.0~ ¦ 2~3 9.43 ¦ 3~4 S O.SX W1 ~ 250 3.26 ¦ 4 5 1.70 I S 2.27 ¦ S
50 i~pm coi~per 500 7.01 1 4 ~.71 1 4 6.19 1 4 750 9.69 j ~ ô.9~ 1 3 ~.99 1 3-4
Claims (26)
1. Polyamide fibre having improved W light stability, said fibre containing a UV light stabilizing package comprising:
(a) a heterocyclic polymeric hindered amine;
(b) an organic hindered phenolic antioxidant; and (c) a third component selected from the group comprising:
a benzotriazole compound; a copper compound; an organic phosphite; and a combination of an organic phosphite and a copper compound.
(a) a heterocyclic polymeric hindered amine;
(b) an organic hindered phenolic antioxidant; and (c) a third component selected from the group comprising:
a benzotriazole compound; a copper compound; an organic phosphite; and a combination of an organic phosphite and a copper compound.
2. The composition of claim 1 wherein said hindered amine is selected from the group comprising: copolymer formed from dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol; poly[[6-[(1,1,3,3-tetramethylbutyl) amino]-5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)imino)]; and poly[(6-morpholino-5-triazine-2,4-diyl)[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylenel(2,2,6,6-tetramethyl-4-piperidyl)imino]].
3. The composition of claim 1 wherein said phenolic antioxidant is selected from the group comprising: 2,6-di-tert-butyl-4-methylphenol; octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate: 2,2'-methylene bis (4-methyl-6-tert-butylphenol); 2,2'-methylene bis (4-ethyl-6-tert-butylphenol),
4,4'-butylidene bis(6-tert-butyl-3-methylphenol); N,N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide);
2,2'-oxamido bis (ethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butanoic acid] glycol ester; triethyleneglycol bis (3-tert-butyl-4-hydroxy-5-methyl-hydrocinnamate): tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]
methane; 1,3,5-trimethyl-2,4,6-tris (3',5'-di-tert-butyl-4'-hydroxybenzyl)-benzene; 3,5-di-tert-butyl-4-hydroxyhydrocinnamic triester with 1,3,5-tris (2-hydroxyethyl)-5-triazine-2,4,6-(1H,3H,5H)-trione; and 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-5-triazine 2,4,6-(1H,3H,5H) trione.
4, The fibre of claim 2 wherein said phenolic antioxidant is selected from the group comprising: 2,6-di-tert-butyl-4-methylphenol; octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; 2,2'-methylene bis (4-methyl-6-tert-butylphenol); 2,2'-methylene bis (4-ethyl-6-tert-butylphenol);
4,4'-butylidene bis (6-tert-butyl-3-methylphenol); N,N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide);
2,2'-oxamido bis (ethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butanoic acid] glycol ester; triethyleneglycol bis (3-tert-butyl-4-hydroxy-5-methyl-hydrocinnamate); tetrakis [methylene (3,5-di tert-butyl-4-hydroxyhydrocinnamate)]
methane; 1,3,5-trimethyl-2,4,6-tris (3',5'-di-tert-butyl-4'-hydroxybenzyl)-benzene; 3,5-di-tert-butyl-4-hydroxy-hydrocinnamic triester with 1,3,5-tris (2-hydroxyethyl)-5-triazine-2,4,6-(1H,3H,5H)-trione; and 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-5-triazine 2,4,6-(1H,3H,5H) trione.
2,2'-oxamido bis (ethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butanoic acid] glycol ester; triethyleneglycol bis (3-tert-butyl-4-hydroxy-5-methyl-hydrocinnamate): tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]
methane; 1,3,5-trimethyl-2,4,6-tris (3',5'-di-tert-butyl-4'-hydroxybenzyl)-benzene; 3,5-di-tert-butyl-4-hydroxyhydrocinnamic triester with 1,3,5-tris (2-hydroxyethyl)-5-triazine-2,4,6-(1H,3H,5H)-trione; and 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-5-triazine 2,4,6-(1H,3H,5H) trione.
4, The fibre of claim 2 wherein said phenolic antioxidant is selected from the group comprising: 2,6-di-tert-butyl-4-methylphenol; octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; 2,2'-methylene bis (4-methyl-6-tert-butylphenol); 2,2'-methylene bis (4-ethyl-6-tert-butylphenol);
4,4'-butylidene bis (6-tert-butyl-3-methylphenol); N,N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide);
2,2'-oxamido bis (ethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butanoic acid] glycol ester; triethyleneglycol bis (3-tert-butyl-4-hydroxy-5-methyl-hydrocinnamate); tetrakis [methylene (3,5-di tert-butyl-4-hydroxyhydrocinnamate)]
methane; 1,3,5-trimethyl-2,4,6-tris (3',5'-di-tert-butyl-4'-hydroxybenzyl)-benzene; 3,5-di-tert-butyl-4-hydroxy-hydrocinnamic triester with 1,3,5-tris (2-hydroxyethyl)-5-triazine-2,4,6-(1H,3H,5H)-trione; and 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-5-triazine 2,4,6-(1H,3H,5H) trione.
5. The fibre of claim 1 wherein said benzotriazole compound is selected from the group comprising: 2(2'-hydroxy-4'-octoxyphenyl)-benzotriazole; 2(2'-hydroxy-5'-t-octylphenyl)-benzotriazole; 2(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole; 2(2'-hydroxy-3'5'-di-t-butylphenyl)-benzotriazole; 2(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole; and 2-(3',5'-bis(1-methyl-1-phenylethyl)-2'-hydroxyphenyl) benzotriazole
6. The fibre of claim 4 wherein said benzotriazole compound is selected from the group comprising: 2(2'-hydroxy-4'-octoxyphenyl)-benzotriazole; 2(2'-hydroxy-5'-t-octylphenyl)-benzotriazole; 2(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole; 2(2'-hydroxy-3'5'-di-t-butylphenyl)-benzotriazole; 2(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole; and 2-(3',5'-bis (1-methyl-1-phenylethyl)-2'-hydroxyphenyl) benzotriazole.
7. The fibre of claim 1 wherein said phosphite compound is selected from the group comprising: tris (nonylphenyl) phosphite; bis (2,4-di-tert-butyl)-pentaerythritol diphosphite; distearyl pentaerythritol diphosphite; tris (2,4-di-tert-butylphenyl) phosphite, and tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylylenediphosphite.
8. The fibre of claim 4 wherein said phosphite compound is selected from the group comprising: tris (nonylphenyl) phosphite; bis (2,4-di-tert-butyl)-pentaerythritol diphosphite; distearyl pentaerythritol diphosphite; tris (2,4-di-tert-butylphenyl) phosphite; and tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylylenediphosphite.
9. The fibre of claim 1 wherein said copper compound contains copper cations in either a +1 or a +2 oxidation state.
10. The fibre of claim 9 wherein said copper compound is selected from the group comprising copper acetate; copper bromide; copper iodide; and copper nitrate.
11. The fibre of claim 4 wherein said copper compound containscopper cations in either a +1 or a +2 oxidation state.
12. The fibre of claim 11 wherein said copper compound is selected from the group comprising copper acetate; copper bromide; copper iodide; and copper nitrate.
13. The fibre of claim 8 wherein said copper compound contains copper cations in either a +1 or a +2 oxidation state.
14. The fibre of claim 13 wherein said copper compound is selected from the group comprising copper acetate; copper bromide; copper iodide; and copper nitrate.
15. A dyed polyamide fibre having improved UV light stability and dye lightfastness, said fibre comprising a dye coated on the surface thereof and a UV light stabilizing package incorporated therein, said package comprising:
(a) a heterocyclic polymeric hindered amine;
(b) an organic hindered phenolic antioxidant;
(c) a third component selected from the group comprising:
an organic phosphite compound; and a combination of an organic phosphite and a copper compound.
(a) a heterocyclic polymeric hindered amine;
(b) an organic hindered phenolic antioxidant;
(c) a third component selected from the group comprising:
an organic phosphite compound; and a combination of an organic phosphite and a copper compound.
16. The fibre of claim 15 wherein said hindered amine is selected from the group comprising: copolymer formed from dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol; poly [[6-[(1,1,3,3-tetramethyl-butyl) amino]-5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)imino]]: and poly[(6-morpholino-5-triazine-2,4-diyl)[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)iminol].
17. The fibre of claim 15 wherein said phenolic antioxidant is selected from the group comprising: 2,6-di-tert-butyl-4-methylphenol; octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; 2,2'-methylene bis(4-methyl-6-tert-butylphenol); 2,2'-methylene bis (4-ethyl-6-tert-butylphenol);
4,4'-butylidene bis (6-tert-butyl-3-methylphenol); N,N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide);
2,2'-oxamido bis (ethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; bis 13,3-bis(4-hydroxy-3-tert-butylphenyl) butanoic acid] glycol ester; triethyleneglycol bis (3-tert-butyl-4-hydroxy-5-methyl-hydrocinnamate); tetraxis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]
methane: 1,3,5-trimethyl-2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-benzene; 3,5-di-tert-butyl-4-hydroxy-hydrocinnamic triester with 1,3,5-tris (2-hydroxyethyl)-5-triazine-2,4,6-(1H,3H,5H)-trione; and 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-5-triazine 2,4,6-(lH,3H,5H) trione.
4,4'-butylidene bis (6-tert-butyl-3-methylphenol); N,N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide);
2,2'-oxamido bis (ethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; bis 13,3-bis(4-hydroxy-3-tert-butylphenyl) butanoic acid] glycol ester; triethyleneglycol bis (3-tert-butyl-4-hydroxy-5-methyl-hydrocinnamate); tetraxis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]
methane: 1,3,5-trimethyl-2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-benzene; 3,5-di-tert-butyl-4-hydroxy-hydrocinnamic triester with 1,3,5-tris (2-hydroxyethyl)-5-triazine-2,4,6-(1H,3H,5H)-trione; and 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-5-triazine 2,4,6-(lH,3H,5H) trione.
18. The fibre of claim 16 wherein said phenolic antioxidant is selected from the group comprising: 2,6-di-tert-butyl-4-methylphenol; octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; 2,2'-methylene bis(4-methyl-6-tert-butylphenol); 2,2'-methylene bis (4-ethyl-6-tert-butylphenol);
4,4'-butylidene bis(6-tert-butyl-3-methylphenol); N,N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide);
2,2'-oxamido bis(ethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; bis [3,3-bis(4-hydroxy-3-tert-butylphenyl)butanoic acid]qlycol ester; triethyleneglycol bis (3-tert-butyl-4-hydroxy-5-methyl-hydrocinnamate); tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]
methane; 1,3,5-trimethyl-2,4,6-tris (3',5'-di-tert-butyl-4'-hydroxybenzyl)-benzene; 3,5-di-tert-butyl-4-hydroxy-hydrocinnamic triester with 1,3,5-tris (2-hydroxyethyl)-5-triazine-2,4,6-(1H,3H,5H)-trione; and 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-5-triazine 2,4,6-(1H,3H,5H) trione.
4,4'-butylidene bis(6-tert-butyl-3-methylphenol); N,N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide);
2,2'-oxamido bis(ethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; bis [3,3-bis(4-hydroxy-3-tert-butylphenyl)butanoic acid]qlycol ester; triethyleneglycol bis (3-tert-butyl-4-hydroxy-5-methyl-hydrocinnamate); tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]
methane; 1,3,5-trimethyl-2,4,6-tris (3',5'-di-tert-butyl-4'-hydroxybenzyl)-benzene; 3,5-di-tert-butyl-4-hydroxy-hydrocinnamic triester with 1,3,5-tris (2-hydroxyethyl)-5-triazine-2,4,6-(1H,3H,5H)-trione; and 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-5-triazine 2,4,6-(1H,3H,5H) trione.
19. The fibre of claim 15 wherein said phosphite compound is selected from the group comprising: tris (nonylphenyl) phosphite; bis (2,4-di-tert-butyl)-pentaerythritol diphosphite; distearyl pentaerythritol diphosphite; tris(2,4-di-tert-butylphenyl) phosphite; and tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylylenediphosphite.
20. The fibre of claim 18 wherein said phosphite compound is selected from the group comprising:
tris(nonylphenyl)phosphite; bis(2,4-di-tert-butyl)-pentaerythritol diphosphite; distearyl pentaerythritol diphosphite; tris(2,4-di-tert-butylphenyl)phosphite; and tetrakis (2,4-di-tert-butylphenyl)4,4'-biphenylylenediphosphite
tris(nonylphenyl)phosphite; bis(2,4-di-tert-butyl)-pentaerythritol diphosphite; distearyl pentaerythritol diphosphite; tris(2,4-di-tert-butylphenyl)phosphite; and tetrakis (2,4-di-tert-butylphenyl)4,4'-biphenylylenediphosphite
21. The fibre of claim 15 wherein said copper compound is selected from copper compounds containing copper cations in either a +1 or a +2 oxidation state.
22. The fibre of claim 21 wherein said copper compound is selected from the group comprising: copper acetate; copper bromide; copper iodide; and copper nitrate.
23. The fibre of claim 18 wherein said copper compound is selected from copper compounds containing copper cations in either a +1 or a +2 oxidation state.
24. The fibre of claim 23 wherein said copper compound is selected from the group comprising: copper acetate; copper bromide; copper iodide; and copper nitrate.
25. The fibre of claim 20 wherein said copper compound is selected from copper compounds containing copper cations in +1 or +2 oxidation state.
26. The fibre of claim 25 wherein said copper compound is selected from the group comprising: copper acetate; copper bromide; copper iodide; and copper nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2064606 CA2064606A1 (en) | 1992-04-01 | 1992-04-01 | Uv light stable polyamide fibre |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2064606 CA2064606A1 (en) | 1992-04-01 | 1992-04-01 | Uv light stable polyamide fibre |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2064606A1 true CA2064606A1 (en) | 1993-10-02 |
Family
ID=4149543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2064606 Abandoned CA2064606A1 (en) | 1992-04-01 | 1992-04-01 | Uv light stable polyamide fibre |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2064606A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5856550A (en) * | 1994-04-05 | 1999-01-05 | Ciba Specialty Chemicals Corporation | Enhancement of the storage stability of organic phosphites and phosphonites |
-
1992
- 1992-04-01 CA CA 2064606 patent/CA2064606A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5856550A (en) * | 1994-04-05 | 1999-01-05 | Ciba Specialty Chemicals Corporation | Enhancement of the storage stability of organic phosphites and phosphonites |
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| Date | Code | Title | Description |
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| FZDE | Dead |