WO1994024344A1 - Low color processing, heat and light stabilizer system for polypropylene fiber - Google Patents

Low color processing, heat and light stabilizer system for polypropylene fiber Download PDF

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Publication number
WO1994024344A1
WO1994024344A1 PCT/IB1994/000056 IB9400056W WO9424344A1 WO 1994024344 A1 WO1994024344 A1 WO 1994024344A1 IB 9400056 W IB9400056 W IB 9400056W WO 9424344 A1 WO9424344 A1 WO 9424344A1
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WO
WIPO (PCT)
Prior art keywords
bis
amino
tert
fiber
piperidine
Prior art date
Application number
PCT/IB1994/000056
Other languages
French (fr)
Inventor
Douglas W. Horsey
Roswell E. King, Iii
Original Assignee
Ciba-Geigy Ag
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Filing date
Publication date
Priority to CA002160574A priority Critical patent/CA2160574C/en
Priority to DE4492361T priority patent/DE4492361T1/en
Priority to SK1272-95A priority patent/SK284817B6/en
Priority to JP52295194A priority patent/JP3424080B2/en
Application filed by Ciba-Geigy Ag filed Critical Ciba-Geigy Ag
Priority to KR1019950704499A priority patent/KR100282620B1/en
Priority to DE4492361A priority patent/DE4492361C2/en
Priority to BR9406876A priority patent/BR9406876A/en
Priority to AU62632/94A priority patent/AU6263294A/en
Priority to NL9420023A priority patent/NL9420023A/en
Priority to RU95120604A priority patent/RU2126065C1/en
Priority to GB9520527A priority patent/GB2292944B/en
Publication of WO1994024344A1 publication Critical patent/WO1994024344A1/en
Priority to NO953932A priority patent/NO309683B1/en
Priority to DK199501109A priority patent/DK175151B1/en
Priority to HK98104631A priority patent/HK1005489A1/en

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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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

  • the instant invention pertains to stabilized polypropylene fiber, free or essentially free of any traditionally used phenolic antioxidant, and having enhanced light stability, enhanced long term heat stability and especially enhanced gas fade resistance.
  • This fiber formu ⁇ lation is stabilized by an effective amount of a mixture of a selected hindered amine, a se ⁇ lected hydroxylamine and a selected phosphite.
  • Polypropylene fiber is traditionally stabilized with a blend of selected phenolic antioxi ⁇ dant, selected phosphite and selected hindered amine light stabilizer.
  • This formulation generally provides adequate processing, heat and light stabilization performance, but does not provide adequate gas fade resistance which is needed to maintain color properties during storage and end-use application.
  • Gas fading is known in the industry as a discoloration re ⁇ sulting from the exposure of plastic articles to an atmosphere containing oxides of nitro ⁇ gen.
  • the components of the instant stabilizer system for polypropylene fibers are generically well-known as stabilizers for a host of organic and polymeric substrates.
  • the components of the instant stabilizer system for polypropylene fiber are a specific combination of selec ⁇ ted 2,2,6,6-tetramethylpiperidine hindered amines, phosphites or phosphorates and N,N- dialkylhydroxylamines, in the absence or essential absence of a phenolic antioxidant.
  • This instant stabilizer formulation provides unexpectedly superior gas fade resistance, and heat and light stability performance properties to the polypropylene fibers which are notorious ⁇ ly difficult to stabilize effectively.
  • the instant phenolic free antioxidant stabilizer system provides the best overall stabilization for polypropylene fiber.
  • Discoloration of polypropy ⁇ lene fibers when exposed to an atmosphere containing oxides of nitrogen, i.e. gas fading conditions, encountered with stabilizer systems containing phenolic antioxidants, makes such systems unacceptable in this important property even though in other performance criteria the phenolic antioxidants perform adequately.
  • the hindered amines are a very important class of light and thermal stabilizers based on compounds having a 2,2,6,6-tetramethylpiperidine moiety somewhere in the molecule. These compounds have achieved great commercial success and are well-known in the art.
  • phosphonites or phosphites such as those described in US-A-4360 617 have also achieved great commercial success as stabilizers.
  • N,N-Dialkylhydroxylamines also are known in the art as seen in US-A-4590 231, US-A-4782 105, US-A-4876 300 and US-A-5 013 510. These compounds are useful as process stabilizers for polyolefins when used alone or in combination with phenolic anti ⁇ oxidants and/or other coadditives, particularly as taught in US-A-4876 300.
  • compositions of the prior art are distinguished from the compositions of the prior art in several important aspects listed below:
  • Hindered phenolic antioxidants plus phosphites combinations have generally poor gas fade resistance
  • Phosphites plus hindered amines lack adequate process stabilization.
  • the instant combination of stabilizers provide all of the required requisites of gas fade resistance and process and thermal stability.
  • the object of this invention is to provide a stabilizer system for polypropylene fiber, in the absence of any traditionally used phenolic antioxidant or in the presence of only very low levels of phenolic antioxidant, which would allow the polypropylene fibers to have en ⁇ hanced light and long term heat stability and especially enhanced gas fade resistance while maintaining process stabilization comparable to any system using phenolic antioxidants.
  • Another object of the instant invention is to provide a method to improve gas fade re- sistance and to reduce color formation in polypropylene fibers by using the instant stabili ⁇ zer system free of phenolic antioxidant.
  • the instant invention pertains to stabilized polypropylene fiber, free or essentially free of any phenolic antioxidant, and having enhanced light stability, enhanced long term heat stability and enhanced gas fade resistance, which fiber is stabilized by a mixture of
  • a hydroxylamine selected from the group consisting of N,N-dioctadecylhydroxylamine
  • N,N-dialkylhydroxylamine of the formula T 1 T 2 NOH where T 1 and T 2 are the all yl mixture found in hydrogenated tallow amine; and the N,N-diallcylhydroxylamine product made by the direct oxidation of N N-di(hydro- genated tallow)amine by the process of US-A-5 013 510 or US-A-4898 901;
  • weight ratio of components (a):(b):(c) is from 1:1:1 to 100:2:1; preferably 10:1:1 to 10:2:1; and most preferably 6:1:1 to 6:2:1.
  • the effective amount of the mixture of stabilizers is from 0.05 to 5 %, preferably 0.1 to 2 %, most preferably 0.15 to 1 %, by weight based on the weight of the fiber.
  • Stabilized polypropylene fiber which are of particular interest are those where the compo ⁇ nent (a) is selected from the group consisting of
  • Stabilized polypropylene fiber which are also of particular interest are those where the component (b) is selected from the group consisting of
  • Stabilized polypropylene fiber which are particularly preferred are those where the com ⁇ ponent (c) is the N,N-dialkylhydroxylamine product made by the direct oxidation of N,N- di(hydrogenated tallow)amine by the process of US-A-5 013 510 or US-A-4898 901.
  • the instant invention also pertains to a binary stabilizer system where the sta ⁇ bilized polypropylene fiber, free or essentially free of any phenolic antioxidant, and having enhanced light stability, enhanced long term heat stability and enhanced gas fade resistance, which fiber is stabilized by a mixture of
  • Binary stabilized polypropylene fiber which are of particular interest are those where the component (I) is selected from the group consisting of
  • Binary stabilized polypropylene fiber which are of particular interest are those where the component (II) is the N,N-dialkylhydroxylamine product made by the direct oxidation of N,N-di(hydrogenated tallow)amine by the process of US-A-5 013 510 or US-A-4 898 901.
  • the effective amount of the mixture of stabilizers is from 0.05 to 5 %, preferably 0.1 to 2 %, most preferably 0.15 to 1 %, by weight based on the weight of the fiber.
  • the instant invention involves a selected mixture of stabilizers which are free or essentially free of any phenolic antioxidants.
  • Some manufacturers of polypropylene add tiny amounts, usually ⁇ 0.01 % by weight of phenolic antioxidant, to aid in the initial manufacture of the polypropylene resin.
  • the amount of phenolic antioxidant remaining in the resin used to prepare polypropylene fiber is far less than the 0.05% by weight of phenolic antioxidant used in the working examples of US-A-4876300.
  • free or essentially free of phenolic anti ⁇ oxidant as used in the context of the instant invention means 0 to 0.01 % by weight of phenolic antioxidant may be present in the instant compositions. No phenolic antioxidant is deliberately added to the instant compositions in order to achieve the stabilization efficacies described.
  • Another most important aspect of the instant invention is to a method for improving gas fade resistance and reducing color formation in stabilized polypropylene fiber by incorpo ⁇ rating therein an effective stabilizing amount of the mixture of stabilizers described above without the loss of any other stabilization property.
  • Still another aspect of the instant invention is to a method for enhancing the resistance to degradation of polypropylene fiber, due to exposure to UV radiation over that which can be achieved by the use of conventional stabilizers alone, by incorporating therein an effec ⁇ tive stabilizing amount of the mixture of stabilizers described above.
  • Yet another aspect of the instant invention is to a method for enhancing the thermal stabi ⁇ lity of polypropylene fiber, over that which can be achieved by the use of conventional stabilizers alone, by incorporating therein an effective stabilizing amount of the mixture of stabilizers described above.
  • the cited hindered amines and phosphites are generally commercially available or can be made by published methods.
  • N,N-dialkylhydroxylamines are prepared by methods disclosed in US-A-4782 105; US-A-4 898 901 and particularly US-A-5 013 510 by the direct oxidation of N,N-di- (hydrogenated tallow)amine by hydrogen peroxide.
  • the polypropylene fiber may also contain other additives such as fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite and other additives, for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame- proofing agents and anti-static agents.
  • additives such as fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite and other additives, for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame- proofing agents and anti-static agents.
  • Conventional stabilization systems such as phenolic antioxidant with phosphite and hindered amine stabilizer, or phosphite with hindered amine stabilizer, can provide excel ⁇ lent stabilization to polypropylene fibers in selected performance areas, but it is only through the use of the instant ternary combination of a selected hindered amine, selected hydroxylamine and selected phosphite that all important performance properties for sta ⁇ bilized polypropylene fibers can be optimized.
  • Polypropylene is used extensively for the manufacture of fiber for residential, commercial and automotive carpeting. White and light-colored fiber can suffer from discoloration due to gas fade discoloration.
  • Polypropylene resin as it is originally manufactured may contain very low levels of phenolic antioxidant for stability till said resin is later fabricated into fiber. In each case some additional stabilizer package must be added to the propylene resin before fabrication into fiber is possible.
  • Hindered phenolic antioxidants are well-known as a potential source of such discoloration by the formation of quinone type chromophores as oxidation products or as the result of environmental exposure to the oxides of nitrogen (known as "gas fade" discoloration).
  • Phenolic antioxidants protect the polymer during high temperature melt processing, extrusion and spinning operations. Phenolic antioxi ⁇ dants further protect the polymer pellets and resultant fiber during storage and final end- use applications.
  • the phenolic antioxidant could be replaced in the instant stabilizer system which is a ternary combination of a selected hindered amine, a selected hydroxylamine and a selected phosphite or a binary combination of a selected hindered amine and a selected hydroxylamine.
  • Said system provides stability in excess of that ob ⁇ tained with conventional stabilizer systems having a phenolic antioxidant component without the discoloration associated with the phenolic antioxidant when the stabilized polypropylene fiber is exposed to gas fading conditions, i.e. in an atmosphere containing the oxides of nitrogen.
  • AO A l,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate
  • HALS 1 the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6- tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine;
  • HALS 2 the polycondensation product of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl- 4-hydroxypiperidine and succinic acid;
  • HALS 3 N,N',N ,, ,N'"-tetralds[4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl)- amino)-s-triazin-2-yl]-l,10-diamino-4,7-diazadecane;
  • HALS 4 the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6- tetramethylpiperidine) and 2,4-dichloro-6-morpholino-s-triazine;
  • HALS 5 polyfmethyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane
  • HALS 6 bis(2,2,6,6-tetramethylpiperidin-4-yl) cyclohexylenedioxydimethyl- malonate
  • HALS 7 l,3,5-tris ⁇ N-cyclohexyl-N-[2-(2,2,6,6-tetramethyl ⁇ iperazin-3-on-4-yl)- ethyl]amino-s-triazine;
  • Phos I tris(2,4-di-tert-butylphenyl) phosphite
  • Phos m 2,2 , ,2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-l,l'-biphenyl-2,2'- diyl) phosphite];
  • Phos IV ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite
  • HA A the N,N-dialkylhydroxylamine product made by the direct oxidation of
  • All additives are designated in % by weight based on the polypropylene. All formulations also contain 0.05% by weight of calcium stearate.
  • Example 1 Process Stabilization of Polypropylene Fiber.
  • Fiber grade polypropylene containing 0.05 % by weight of calcium stearate, is dry blen ⁇ ded with the test additives and then melt compounded at 246°C into pellets.
  • the pelletized fully formulated resin is then spun at 274°C into fiber using a Hills laboratory model fiber extruder.
  • the spun tow of 41 filaments is stretched at a ratio of 1: 3.2 to give a final denier of 615/41.
  • melt flow rates of the formulated pellets before spinning and of the spun fiber tow after spinning are determined by ASTM 1238-86. The closer are the melt flow rates before and after spinning, the more effective is the process stabilization efficacy of the stabilizer system.
  • processing stability data are given in Tables 1, 2, 3 and 4 below.
  • HALS 2 0.30 % Phos I 0.05 % 13.8 18.3 HAA 0.05 %
  • HALS 2 0.05 % Phos I 0.05 % 14.4 18.7 HAA 0.05 %
  • HALS 3 0.30 % Phos I 0.05 % 14.2 17.5 HAA 0.05 %
  • Example 1 Melt flow differences resulting from insufficient processing stability can be even more evident when the polypropylene is spun under more severe processing conditions.
  • Example 1 the polypropylene is spun at 274°C. However, it is not unusual for polypropylene to be spun at much higher temperature at 302°C.
  • the melt flow values of polypropylene spun at such tempe ⁇ ratures are shown in the Tables 5, 6, 7 or 8 below.
  • HALS 2 0.05 % Phos I 0.05 % 13.7 17.4 HAA 0.05 %
  • HALS 2 0.05 % Phos I 0.10% 13.6 16.1 HAA 0.05 %
  • HALS 3 0.05 % Phos I 0.05 % 12.4 16.9 HAA 0.05 %
  • Example 3 Light Stabilization of Polypropylene Fiber.
  • the fibers are also exposed to UV light and to long term thermal aging under standard conditions.
  • Socks knitted from the stabilized polypropylene fibers are exposed in an Atlas Xenon- Arc-WeatherOmeter using the SAE J1885 Interior Automotive conditions at 89°C, 0.55 kW/cm 2 at 340 nm with no spray cycle. Failure in this test is determined by the observa- tion of the physical failure of the sock when it is "scratched" with a blunt glass rod. The longer it takes for this catastrophic failure to occur, the more effective is the stabilizer system. The days to failure are given in Tables 9, 10, 11 and 12 below for each of the sta ⁇ bilization systems.
  • HALS 3 0.30 % Phos I 0.05 % 37 HA A 0.05 %
  • Example 4 Long Term Heat Stability of Polypropylene Fiber.
  • HALS 2 0.30 % Phos I 0.05 % 72 HA A 0.05 %
  • HALS 3 0.30 % Phos I 0.05 % 75 HA A 0.05 %
  • Examples 5-6 show that, in regards to gas fade resistance, the instant stabilization mixture is far superior as measured by Delta E values where low numbers indicate less color. The numerical differences shown are significant, and the samples can be easily differentiated visually.
  • Example 5 Gas Fade Resistance or Color Stability of Polypropylene Fiber.
  • HALS 2 0.30 % Phos I 0.09 % 1.6 1.5 HAA 0.01 %
  • HALS 2 0.30 % Phos I 0.05 % 1.5 1.9 HAA 0.05 %
  • HALS 2 0.30 % AOA 0.05 % 3.9 5.3 Phos I 0.09 % HAA 0.01 %
  • HALS 2 0.30 % AOA 0.05 % Phos I 0.05 % 1.9 3.7 HAA 0.05 %
  • HALS 2 0.05 % Phos I 0.09 % 1.6 1.5 HAA 0.01 %
  • HALS 2 0.05 % Phos I 0.05 % 1.0 1.3 HAA 0.05 %
  • HALS 2 0.05 % AOA . 0.05 % 3.8 4.9 Phos I 0.09 % HAA 0.01 %
  • HALS 2 0.05 % AOA 0.05 % Phos I 0.05 % 2.0 3.9 HAA 0.05 % Table 20:
  • HALS 3 0.30 % Phos I 0.05 % 1.7 1.9 HAA 0.05 %
  • HALS 3 0.30 % AOA 0.05 % 4.8 6.7 Phos I 0.09 % HAA 0.01 %
  • HALS 3 0.30 % AOA 0.05 % Phos I 0.05 % 3.1 5.3 HAA 0.05 %
  • HALS 3 0.05 % Phos I 0.05 % 1.2 1.3 HAA 0.05 %
  • HALS 3 0.05 % AOA 0.05 % 4.0 5.3 Phos I 0.09 % HAA 0.01 %
  • HALS 2 0.05 % Phos II 0.05 % 1.5 1.8 HA A 0.05 %
  • HALS 2 0.05 % AO A 0.05 % 1.9 3.1 Phos H 0.05 % HA A 0.05 %
  • HALS 4 0.30 % Phos I 0.05 % 1.2 HAA 0.05 %
  • HALS 5 0.30 % Phos I 0.05 % 1.0 HAA 0.05 %
  • HALS 6 0.30 % Phos I 0.05 % 1.0 HAA 0.05 %
  • melt flow differences resulting from insufficient processing stability are quite evident when toe polypropylene is spun under severe processing conditions. This is particularly evident when polypropylene is spun at 302°C. The lower the melt flow rates are the more effective is the process stabilization efficacy of the stabilizer system (see also example 1). The melt flow values of polypropylene spun at that temperature are shown in the Tables 29, 30 and 31 below.
  • HALS 1 0.05 % Phos I 0.05 % 18 HA A 0.05 %
  • HALS 2 0.05 % Phos I 0.10 % 15 AO A 0.05 %
  • HALS 2 0.05 % Phos I 0.05 % 19 HA A 0.05 %
  • HALS 2 0.05 % 18 HA A 0.05 %
  • HALS 3 0.05 % Phos I 0.05 % 17 HA A 0.05 %
  • HALS 3 0.05 % 17 HA A 0.05 %

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Abstract

Blends of long chain N,N-dialkylhydroxylamines, selected phosphites and selected hindered amines are surprisingly effective in providing processing, long term heat aging and light stability performance and especially gas fade resistance to polypropylene fibers in the absence of a traditionally used phenolic antioxidant.

Description

Low Color Processing, Heat and Light Stabilizer System for Polypropylene Fiber
The instant invention pertains to stabilized polypropylene fiber, free or essentially free of any traditionally used phenolic antioxidant, and having enhanced light stability, enhanced long term heat stability and especially enhanced gas fade resistance. This fiber formu¬ lation is stabilized by an effective amount of a mixture of a selected hindered amine, a se¬ lected hydroxylamine and a selected phosphite.
Polypropylene fiber is traditionally stabilized with a blend of selected phenolic antioxi¬ dant, selected phosphite and selected hindered amine light stabilizer. This formulation generally provides adequate processing, heat and light stabilization performance, but does not provide adequate gas fade resistance which is needed to maintain color properties during storage and end-use application. There is a long-felt need in the marketplace for a stabilizer system which can prevent this gas fading and color formation associated with the use of phenolic antioxidants. Gas fading is known in the industry as a discoloration re¬ sulting from the exposure of plastic articles to an atmosphere containing oxides of nitro¬ gen.
The components of the instant stabilizer system for polypropylene fibers are generically well-known as stabilizers for a host of organic and polymeric substrates. The components of the instant stabilizer system for polypropylene fiber are a specific combination of selec¬ ted 2,2,6,6-tetramethylpiperidine hindered amines, phosphites or phosphorates and N,N- dialkylhydroxylamines, in the absence or essential absence of a phenolic antioxidant. This instant stabilizer formulation provides unexpectedly superior gas fade resistance, and heat and light stability performance properties to the polypropylene fibers which are notorious¬ ly difficult to stabilize effectively. The instant phenolic free antioxidant stabilizer system provides the best overall stabilization for polypropylene fiber. Discoloration of polypropy¬ lene fibers, when exposed to an atmosphere containing oxides of nitrogen, i.e. gas fading conditions, encountered with stabilizer systems containing phenolic antioxidants, makes such systems unacceptable in this important property even though in other performance criteria the phenolic antioxidants perform adequately. The hindered amines are a very important class of light and thermal stabilizers based on compounds having a 2,2,6,6-tetramethylpiperidine moiety somewhere in the molecule. These compounds have achieved great commercial success and are well-known in the art.
Likewise, phosphonites or phosphites such as those described in US-A-4360 617 have also achieved great commercial success as stabilizers.
N,N-Dialkylhydroxylamines also are known in the art as seen in US-A-4590 231, US-A-4782 105, US-A-4876 300 and US-A-5 013 510. These compounds are useful as process stabilizers for polyolefins when used alone or in combination with phenolic anti¬ oxidants and/or other coadditives, particularly as taught in US-A-4876 300. Although US-A-4876300 teaches generically that N,N-diallcylhydroxylamines can be used in com¬ bination with phenolic antioxidants, hindered amines, phosphites, UV absorbers and other additives, there is no specific disclosure that polypropylene fibers can be beneficially sta- bil d by specific combinations of selected hindered amines, phosphites or phosphonites and N,N-dialkylhydroxylamines. Thus the instant invention is essentially a selection from within the broad generic scope of US-A-4876300.
However, the instant composition is distinguished from the compositions of the prior art in several important aspects listed below:
1. Hindered phenolic antioxidants plus phosphites combinations have generally poor gas fade resistance;
2. Phosphites alone lack adequate process and thermal stabilization efficacy; and
3. Phosphites plus hindered amines lack adequate process stabilization.
The instant combination of stabilizers provide all of the required requisites of gas fade resistance and process and thermal stability.
The object of this invention is to provide a stabilizer system for polypropylene fiber, in the absence of any traditionally used phenolic antioxidant or in the presence of only very low levels of phenolic antioxidant, which would allow the polypropylene fibers to have en¬ hanced light and long term heat stability and especially enhanced gas fade resistance while maintaining process stabilization comparable to any system using phenolic antioxidants.
Another object of the instant invention is to provide a method to improve gas fade re- sistance and to reduce color formation in polypropylene fibers by using the instant stabili¬ zer system free of phenolic antioxidant.
The instant invention pertains to stabilized polypropylene fiber, free or essentially free of any phenolic antioxidant, and having enhanced light stability, enhanced long term heat stability and enhanced gas fade resistance, which fiber is stabilized by a mixture of
a) a hindered amine selected from the group consisting of
the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl- piperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine; the polycondensation product of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxy- piperidine and succinic acid;
N,N' ,N" ,N' "-tetraMs[4,6-bis(butyl-(2,2,6,6-teframemylpiperidin-4-yl)amino)-s- triazin-2-yl] -1,10-diamino-4,7-diazadecane ; the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl- piperidine) and 2,4-dichloro-6-morpholino-s-triazine; poly[methyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane; bis(2,2,6,6-tetramethylpiperidin-4-yl) cyclohexylenedioxydimethylmalonate; l,3,5-tris{N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpipera^-3-on-4-yl)ethyl]amino-s- triazine; the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl- piperidine) and 2,4-dichloro-6-cyclohexylamino-s-triazine; and poly{N-[4,6-bis(butyl-(2,2,6,6-teframet yl-piperidin-4-yl)amino)-s-triazin-2-yl]- l,4,7-triazanonane}-o>N,,-[4,6-bis(butyl-(2,2,6,6-tetramemylpiperidin-4-yl)ainino)-s- triazin-2-yl]amine;
b) a phosphite selected from the group consisting of
tris(2,4-di-tert-butylphenyl) phosphite;
3,9-di(2,4-di-tert-butylphenyl)-2,4,8,10-tetraoxa-3,9-diphospha[5.5]undecane;
Figure imgf000005_0001
(3,3',5,5'-tetra-tert-butyl-l,r-biphenyl-2,2'-diyl) phosphite]; ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite; and tetrakis(2,4-di-tert-butylphenyl)-4,4' -bis(diphenylene)phosphonite ; and
c) a hydroxylamine selected from the group consisting of N,N-dioctadecylhydroxylamine;
N,N-dialkylhydroxylamine of the formula T1T2NOH where T1 and T2 are the all yl mixture found in hydrogenated tallow amine; and the N,N-diallcylhydroxylamine product made by the direct oxidation of N N-di(hydro- genated tallow)amine by the process of US-A-5 013 510 or US-A-4898 901;
wherein the weight ratio of components (a):(b):(c) is from 1:1:1 to 100:2:1; preferably 10:1:1 to 10:2:1; and most preferably 6:1:1 to 6:2:1.
The effective amount of the mixture of stabilizers is from 0.05 to 5 %, preferably 0.1 to 2 %, most preferably 0.15 to 1 %, by weight based on the weight of the fiber.
Stabilized polypropylene fiber which are of particular interest are those where the compo¬ nent (a) is selected from the group consisting of
the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl- piperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine; the polycondensation product of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxy- piperidine and succinic acid;
N,N' ,N" ,N' ,,-tetrakis[4,6-bis(butyl-(2,2,6,6-teframethylpiperidin-4-yl)amino)-s- triazin-2-yl]-l,10-diamino-4,7-diazadecane; the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl- piperidine) and 2,4-dichloro-6-morpholino-s-triazine; poly[methyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane; bis(2,2,6,6-tetramethylpiperidin-4-yl) cyclohexylenedioxydimethylmalonate; and lt3,5-tris{N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)ethyl]amino-s- triazine.
Stabilized polypropylene fiber which are also of particular interest are those where the component (b) is selected from the group consisting of
tris(2,4-di-tert-butylphenyl) phosphite;
3,9-di(2,4-di-tert-butylρhenyl)-2,4,8,10-tetraoxa-3,9-diphospha[5.5]undecane; 2,2,,2"-nitrilo-tris[ethyl (3,3',5,5'-tetra-tert-butyl-l,l'-biρhenyl-2,2'-diyl) phosphite]; and ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite.
Stabilized polypropylene fiber which are particularly preferred are those where the com¬ ponent (c) is the N,N-dialkylhydroxylamine product made by the direct oxidation of N,N- di(hydrogenated tallow)amine by the process of US-A-5 013 510 or US-A-4898 901.
Additionally, the instant invention also pertains to a binary stabilizer system where the sta¬ bilized polypropylene fiber, free or essentially free of any phenolic antioxidant, and having enhanced light stability, enhanced long term heat stability and enhanced gas fade resistance, which fiber is stabilized by a mixture of
I) a hindered amine selected from the group consisting of
the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl- piperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine; the polycondensation product of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxy- piperidine and succinic acid;
N,N' ,N" ,N' "-tetralris[4,6-bis(butyl-(2,2,6,6-teframethylpiperidin-4-yl)amino)-s- triazin-2-yl]-l,10-diamino-4,7-diazadecane; the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl- piperidine) and 2,4-dichloro-6-morpholino-s-triazine; poly[methyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane; bis(2,2,6,6-tetramethylpiperidin-4-yl) cyclohexylenedioxydimethylmalonate; l,3,5- s{N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)ethyl]amino- s-triazine; and the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl- piperidine) and 2,4-dichloro-6-cyclohexylamino-s-triazine; and
II) a hydroxylamine selected from the group consisting of
N,N-dioctadecylhydroxylamine;
N,N-dialkylhydroxylamine of the formula T^NOH where Tx and T2 are the allcyl mixture found in hydrogenated tallow amine; and the N,N-diallcylhydroxylamine product made by the direct oxidation of N,N-di(hy- drogenated tallow)amine by the process of US-A-5 013 510 or US-A4898 901; wherein the weight ratio of components (I):(II) is from 100:1 to 1:2; preferably 10:1 to 1:1; and most preferably 5:1 to 3:1.
Binary stabilized polypropylene fiber which are of particular interest are those where the component (I) is selected from the group consisting of
the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl- piperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine; the polycondensation product of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxy- piperidine and succinic acid; and
N,N' ,N" ,N' "-tetralris[4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino)-s- triazin-2-yl] -1,10-diamino-4,7-diazadecane.
Binary stabilized polypropylene fiber which are of particular interest are those where the component (II) is the N,N-dialkylhydroxylamine product made by the direct oxidation of N,N-di(hydrogenated tallow)amine by the process of US-A-5 013 510 or US-A-4 898 901.
The effective amount of the mixture of stabilizers is from 0.05 to 5 %, preferably 0.1 to 2 %, most preferably 0.15 to 1 %, by weight based on the weight of the fiber.
The instant invention involves a selected mixture of stabilizers which are free or essentially free of any phenolic antioxidants. Some manufacturers of polypropylene add tiny amounts, usually <0.01 % by weight of phenolic antioxidant, to aid in the initial manufacture of the polypropylene resin. The amount of phenolic antioxidant remaining in the resin used to prepare polypropylene fiber is far less than the 0.05% by weight of phenolic antioxidant used in the working examples of US-A-4876300. As the phrase free or essentially free of phenolic anti¬ oxidant as used in the context of the instant invention means 0 to 0.01 % by weight of phenolic antioxidant may be present in the instant compositions. No phenolic antioxidant is deliberately added to the instant compositions in order to achieve the stabilization efficacies described.
Another most important aspect of the instant invention is to a method for improving gas fade resistance and reducing color formation in stabilized polypropylene fiber by incorpo¬ rating therein an effective stabilizing amount of the mixture of stabilizers described above without the loss of any other stabilization property.
Still another aspect of the instant invention is to a method for enhancing the resistance to degradation of polypropylene fiber, due to exposure to UV radiation over that which can be achieved by the use of conventional stabilizers alone, by incorporating therein an effec¬ tive stabilizing amount of the mixture of stabilizers described above.
Yet another aspect of the instant invention is to a method for enhancing the thermal stabi¬ lity of polypropylene fiber, over that which can be achieved by the use of conventional stabilizers alone, by incorporating therein an effective stabilizing amount of the mixture of stabilizers described above.
The cited hindered amines and phosphites are generally commercially available or can be made by published methods.
The N,N-dialkylhydroxylamines are prepared by methods disclosed in US-A-4782 105; US-A-4 898 901 and particularly US-A-5 013 510 by the direct oxidation of N,N-di- (hydrogenated tallow)amine by hydrogen peroxide.
The polypropylene fiber may also contain other additives such as fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite and other additives, for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame- proofing agents and anti-static agents.
Conventional stabilization systems, such as phenolic antioxidant with phosphite and hindered amine stabilizer, or phosphite with hindered amine stabilizer, can provide excel¬ lent stabilization to polypropylene fibers in selected performance areas, but it is only through the use of the instant ternary combination of a selected hindered amine, selected hydroxylamine and selected phosphite that all important performance properties for sta¬ bilized polypropylene fibers can be optimized.
Polypropylene is used extensively for the manufacture of fiber for residential, commercial and automotive carpeting. White and light-colored fiber can suffer from discoloration due to gas fade discoloration. Polypropylene resin as it is originally manufactured may contain very low levels of phenolic antioxidant for stability till said resin is later fabricated into fiber. In each case some additional stabilizer package must be added to the propylene resin before fabrication into fiber is possible. Hindered phenolic antioxidants are well-known as a potential source of such discoloration by the formation of quinone type chromophores as oxidation products or as the result of environmental exposure to the oxides of nitrogen (known as "gas fade" discoloration).
It is therefore desirable to remove the phenolic antioxidant component from the polypro¬ pylene fiber. Unfortunately when this has been done in the past, other properties related to polymer stability are adversely effected. Phenolic antioxidants protect the polymer during high temperature melt processing, extrusion and spinning operations. Phenolic antioxi¬ dants further protect the polymer pellets and resultant fiber during storage and final end- use applications.
Surprisingly, it was found that the phenolic antioxidant could be replaced in the instant stabilizer system which is a ternary combination of a selected hindered amine, a selected hydroxylamine and a selected phosphite or a binary combination of a selected hindered amine and a selected hydroxylamine. Said system provides stability in excess of that ob¬ tained with conventional stabilizer systems having a phenolic antioxidant component without the discoloration associated with the phenolic antioxidant when the stabilized polypropylene fiber is exposed to gas fading conditions, i.e. in an atmosphere containing the oxides of nitrogen.
The following examples are presented for the pmpose of illustration only and are not to be construed to limit the nature or scope of the instant invention in any manner whatsoever.
Test Compounds:
AO A = l,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate;
HALS 1 = the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6- tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine;
HALS 2 = the polycondensation product of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl- 4-hydroxypiperidine and succinic acid;
HALS 3 = N,N',N,,,N'"-tetralds[4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl)- amino)-s-triazin-2-yl]-l,10-diamino-4,7-diazadecane;
HALS 4 = the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6- tetramethylpiperidine) and 2,4-dichloro-6-morpholino-s-triazine;
HALS 5 = polyfmethyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane;
HALS 6 = bis(2,2,6,6-tetramethylpiperidin-4-yl) cyclohexylenedioxydimethyl- malonate;
HALS 7 = l,3,5-tris{N-cyclohexyl-N-[2-(2,2,6,6-tetramethylρiperazin-3-on-4-yl)- ethyl]amino-s-triazine;
Phos I = tris(2,4-di-tert-butylphenyl) phosphite;
Phos π = 3,9-di(2,4-di-tert-butylphenyl)-2,4,8,10-tetraoxa-3,9-diphospha[5.5]unde- cane;
Phos m = 2,2,,2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-l,l'-biphenyl-2,2'- diyl) phosphite];
Phos IV = ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite; and
HA A = the N,N-dialkylhydroxylamine product made by the direct oxidation of
N,N-di(hydrogenated tallow)amine by the process of US-A-5 013 510 or US-A-4 898 901.
All additives are designated in % by weight based on the polypropylene. All formulations also contain 0.05% by weight of calcium stearate.
Example 1: Process Stabilization of Polypropylene Fiber.
Fiber grade polypropylene, containing 0.05 % by weight of calcium stearate, is dry blen¬ ded with the test additives and then melt compounded at 246°C into pellets. The pelletized fully formulated resin is then spun at 274°C into fiber using a Hills laboratory model fiber extruder. The spun tow of 41 filaments is stretched at a ratio of 1: 3.2 to give a final denier of 615/41.
The melt flow rates of the formulated pellets before spinning and of the spun fiber tow after spinning are determined by ASTM 1238-86. The closer are the melt flow rates before and after spinning, the more effective is the process stabilization efficacy of the stabilizer system. The processing stability data are given in Tables 1, 2, 3 and 4 below.
Table 1:
Melt Flow Rate
Stabilizer Amount
Pellets Fiber
HALS l 0.30 % Phos I 0.09 % 15.4 20.7 HA A 0.01 %
HALS l 0.30 % Phos I 0.05 % 14.9 19.6 HA A 0.05 %
HALS l 0.05 % Phos I 0.09 % 13.6 17.7 HA A 0.01 %
HALS l 0.05 % J Phos I 0.05 % 13.6 18.8 HA A 0.05 %
AO A 0.05 % HALS l 0.05 % 14.3 Phos I 0.05 % 19.3 HA A 0.05 %
Table 2:
Melt Flow Rate
Stabilizer Amount
Pellets Fiber
HALS 2 0.30 % Phos I 0.09 % 13.7 18.6 HAA 0.01 %
HALS 2 0.30 % Phos I 0.05 % 13.8 18.3 HAA 0.05 %
HALS 2 0.05 % Phos I 0.09 % 13.4 17.8 HAA 0.01 %
HALS 2 0.05 % Phos I 0.05 % 14.4 18.7 HAA 0.05 %
AOA 0.05 % HALS 2 0.05 % 12.9 18.1 Phos I 0.05 % HAA 0.05 %
Table 3:
Melt Flow Rate
Stabilizer Amount
Pellets Fiber
HALS 3 0.30 % Phos I 0.09 % 13.3 19.3 HAA 0.01 %
HALS 3 0.30 % Phos I 0.05 % 14.2 17.5 HAA 0.05 %
HALS 3 0.05 % Phos I 0.09 % 14.3 18.6 HAA 0.01 %
HALS 3 0.05 % Phos I 0.05 % 13.7 18.4 HAA 0.05 %
AOA 0.05 % HALS3 0.05 % 12.8 17.5 Phos I 0.05 % HAA 0.05 % Table 4:
Melt Flow Rate
Stabilizer Amount
Pellets Fiber
HALS 2 0.05 %
Phos H 0.05 % 12.7 16.9
HA A 0.05 %
AO A 0.05 % HALS 2 0.05 % Phos π 0.05 % 12.9 16.2 HA A 0.05 %
Inspection of the data given above shows that the instant formulations containing selected hindered amines, phosphites and hydroxylamines provide excellent process stabilization to polypropylene fully comparable to stabilizer systems containing phenolic antioxidants.
Example 2: Process Stabilization of Polypropylene Fiber
Melt flow differences resulting from insufficient processing stability can be even more evident when the polypropylene is spun under more severe processing conditions. In Example 1 the polypropylene is spun at 274°C. However, it is not unusual for polypropylene to be spun at much higher temperature at 302°C. The melt flow values of polypropylene spun at such tempe¬ ratures are shown in the Tables 5, 6, 7 or 8 below.
Table 5:
Melt Flow Rate
Stabilizer Amount Fiber Spun Fiber Spun at274°C at 302°C
Phos I 0.15% 14.6 26.9
Phos I 0.10% 13.3 15.5 AOA 0.05 %
Phos I 0.05 % 12.7 16.1 AOA 0.05 %
Phos I 0.10% 13.5 16.2 HAA 0.05 %
HALS 2 0.05 % Phos I 0.10% 15.7 31.9
HALS 2 0.05 % Phos I 0.10% 14.3 16.3 AOA 0.05 %
HALS 2 0.05 % Phos I 0.05 % 13.7 17.4 HAA 0.05 %
HALS 2 0.05 % Phos I 0.10% 13.6 16.1 HAA 0.05 %
Table 6:
Melt Flow Rate
Stabilizer Amount Fiber Spun Fiber Spun at 274°C at 302°C
PhosH 0.15 % 13.7 20.1
PhosH 0.10% 13.0 16.5 AOA 0.05 %
HALS 2 0.05 % 15.2 22.2 PhosH 0.10%
HALS 2 0.05 %
PhosH 0.10% 12.2 15.5
AOA 0.05 %
HALS 2 0.05 %
PhosH 0.05 % 12.4 15.5
HAA 0.05 %
HALS 2 0.05 %
PhosH 0.10% 12.7 15.6
HAA 0.05 %
Table 7:
Melt Row Rate
Stabilizer Amount Fiber Spun Fiber Spun at274°C at 302°C
Phos I 0.15% 14.6 26.9
Phos I 0.10% 13.3 15.5 AOA 0.05 %
HALS 3 0.05 % 14.8 31.4 Phos I 0.10%
HALS 3 0.05 % Phos I 0.10% 13.5 15.1 AOA 0.05 %
HALS 3 0.05 % Phos I 0.05 % 12.4 16.9 HAA 0.05 %
HALS 3 0.05 % Phos I 0.10% 12.9 16.7 HAA 0.05 %
Table 8:
Melt Row Rate
Stabilizer Amount Fiber Spun Fiber Spun at 274°C at 302°C
Phos π 0.15 % 13.7 20.1
Phos II 0.10 % 13.0 16.5 AO A 0.05 %
HALS 3 0.05 % 14.1 22.8 Phos H 0.10 %
HALS 3 0.05 %
Phos H 0.05 % 13.1 14.9
HA A 0.05 %
HALS 3 0.05 %
Phos H 0.10 % 12.5 15.4
HA A 0.05 %
The data in Tables 5, 6, 7 and 8 clearly show that in a conventional stabilizer system a combination of phenolic antioxidant and phosphite provide good processing stability. The removal of the phenolic antioxidant in the presence or absence of a hindered amine results in a significant loss in process stabilization. However, the substitution of a hydroxylamine in place of the phenolic antioxidant yields process stabilization fully comparable to that provided by the phenolic antioxidant-phosphite system.
As is seen in Example 5, however, the presence of phenolic antioxidant in stabilizer systems has a detrimental effect on gas fade resistance.
Example 3: Light Stabilization of Polypropylene Fiber.
The fibers are also exposed to UV light and to long term thermal aging under standard conditions.
Socks knitted from the stabilized polypropylene fibers are exposed in an Atlas Xenon- Arc-WeatherOmeter using the SAE J1885 Interior Automotive conditions at 89°C, 0.55 kW/cm2 at 340 nm with no spray cycle. Failure in this test is determined by the observa- tion of the physical failure of the sock when it is "scratched" with a blunt glass rod. The longer it takes for this catastrophic failure to occur, the more effective is the stabilizer system. The days to failure are given in Tables 9, 10, 11 and 12 below for each of the sta¬ bilization systems.
Table 9:
Stabilizer Amount Days to Failure in the WeatherOmeter
HALS l 0.30 % Phos I 0.09 % 34 HA A 0.01 %
HALS l 0.30 % Phos I 0.05 % 38 HA A 0.05 %
HALS l 0.30 % AO A 0.05 % Phos I 0.05 % 38 HA A 0.05 %
HALS l 0.30 % AO A 0.05 % 28 Phos I 0.10 %
Table 10:
Stabilizer Amount Days to Failure in the WeatherOmeter
HALS 2 0.30 % Phos I 0.09 % 23 HA A 0.01 %
HALS 2 0.30 % Phos I 0.05 % 30 HA A 0.05 % Table 11:
Stabilizer Amount Days to Failure in the WeatherOmeter
HALS 3 0.30 % Phos I 0.09 % 38 HA A 0.01 %
HALS 3 0.30 % Phos I 0.05 % 37 HA A 0.05 %
Table 12:
Stabilizer Amount Days to Failure in the WeatherOmeter
HALS 2 0.05 %
Phos π 0.05 % 9
HA A 0.05 %
Example 4: Long Term Heat Stability of Polypropylene Fiber.
In the long term heat aging at 120°C, other knitted socks of the stabilized polypropylene fiber are exposed in a forced draft oven equipped with a rotating carousel. Again, failure is determined as described above. The longer it takes for such catastrophic failure to occur, the more efficacious is the stabilizer system. The test data are given in Tables 13, 14 and 15 below.
Table 13:
Stabilizer Amount Days to Failure at 120°C
HALS l 0.30 % Phos I 0.09 % 65 HA A 0.01 %
HALS l 0.30 % Phos I 0.05 % 61 HA A 0.05 % Table 14:
Stabilizer Amount Days to Failure at 120°C
HALS 2 0.30 % Phos I 0.09 % 40 HA A 0.01 %
HALS 2 0.30 % Phos I 0.05 % 72 HA A 0.05 %
Table 15:
Days to Failure
Stabilizer Amount at 120°C
HALS 3 0.30 % Phos I 0.09 % 68 HA A 0.01 %
HALS 3 0.30 % Phos I 0.05 % 75 HA A 0.05 %
Examples 5-6 show that, in regards to gas fade resistance, the instant stabilization mixture is far superior as measured by Delta E values where low numbers indicate less color. The numerical differences shown are significant, and the samples can be easily differentiated visually.
Example 5: Gas Fade Resistance or Color Stability of Polypropylene Fiber.
Other knitted socks of the stabilized polypropylene fiber are exposed to oxides of nitrogen in an Exposure Chamber using the AATCC Test Method 23-1988, "Colorfastoess to Burnt Gas Fumes" for 3 and 7 "cycles". Test specimens are removed from the chamber and assessed for change in color (Delta E color scale) on an Applied Color Systems Model CS-5 colorimeter (D65 illuminant, 2° observer). Low Delta E values indicate less color and better stabilization. The test data are given in Tables 16, 17, 18, 19, 20, 21 and 22 below. Table 16:
Delta E Color after Cycle
Stabilizer Amount
3 7
HALSl 0.30 % Phos I 0.09 % 2.4 2.8 HAA 0.01 %
HALSl 0.30 % Phos I 0.05 % 2.3 2.9 HAA 0.05 %
HALSl 0.30 % AOA 0.05 % 5.7 Phos I 0.09 % 6.7 HAA 0.01 %
HALSl 0.30 % AOA 0.05 % Phos I 0.05 % 4.3 6.1 HAA 0.05 %
Table 17:
Delta E Color after Cycle
Stabilizer Amount
3 7
HALSl 0.05 % Phos I 0.09 % 1.9 1.5 HAA 0.01 %
HALSl 0.05 % Phos I 0.05 % 1.8 1.9 HAA 0.05 %
HALSl 0.05 % AOA 0.05 % 3.8 5.2 Phos I 0.09 % HAA 0.01 %
HALSl 0.05 % AOA 0.05 % Phos I 0.05 % 3.2 5.0 HAA 0.05 % Table 18:
Delta E Color after Cycle
Stabilizer Amount
3 7
HALS 2 0.30 % Phos I 0.09 % 1.6 1.5 HAA 0.01 %
HALS 2 0.30 % Phos I 0.05 % 1.5 1.9 HAA 0.05 %
HALS 2 0.30 % AOA 0.05 % 3.9 5.3 Phos I 0.09 % HAA 0.01 %
HALS 2 0.30 % AOA 0.05 % Phos I 0.05 % 1.9 3.7 HAA 0.05 %
Table 19:
Delta E Color after Cycle
Stabilizer Amount
3 7
HALS 2 0.05 % Phos I 0.09 % 1.6 1.5 HAA 0.01 %
HALS 2 0.05 % Phos I 0.05 % 1.0 1.3 HAA 0.05 %
HALS 2 0.05 % AOA . 0.05 % 3.8 4.9 Phos I 0.09 % HAA 0.01 %
HALS 2 0.05 % AOA 0.05 % Phos I 0.05 % 2.0 3.9 HAA 0.05 % Table 20:
Delta E Color after Cycle
Stabilizer Amount
3 7
HALS 3 0.30 % Phos I 0.09 % 2.4 2.3 HAA 0.01 %
HALS 3 0.30 % Phos I 0.05 % 1.7 1.9 HAA 0.05 %
HALS 3 0.30 % AOA 0.05 % 4.8 6.7 Phos I 0.09 % HAA 0.01 %
HALS 3 0.30 % AOA 0.05 % Phos I 0.05 % 3.1 5.3 HAA 0.05 %
Table 21:
Delta E Color after Cycle
Stabilizer Amount
3 7
HALS 3 0.05 % Phos I 0.09 % 1.9 1.6 HAA 0.01 %
HALS 3 0.05 % Phos I 0.05 % 1.2 1.3 HAA 0.05 %
HALS 3 0.05 % AOA 0.05 % 4.0 5.3 Phos I 0.09 % HAA 0.01 %
HALS 3 0.05 % AOA 0.05 % Phos I 0.05 % 2.3 4.6 HAA 0.05 % Table 22:
Delta E Color after Cycle
Stabilizer Amount
3 7
HALS 2 0.05 % Phos II 0.05 % 1.5 1.8 HA A 0.05 %
HALS 2 0.05 % AO A 0.05 % 1.9 3.1 Phos H 0.05 % HA A 0.05 %
Example 6: Gas Fade Resistance or Color Stability of Polypropylene Fiber
Other knitted socks of the stabilized polypropylene fiber are exposed to oxides of nitrogen in an Exposure Chamber using the AATCC Test Method 23-1988, "Colorfastoess to Burnt Gas Fumes" for 3 "cycles". Test specimens are removed from the chamber and assessed for change in color (Delta E color scale) on an Applied Color Systems Model CS-5 colorimeter (D65 illuminant, 2° observer). The test data are given in Tables 23, 24 and 25 below. Low Delta E values indicate less color and better stabilization.
Table 23:
Stabilizer Amount Delta E Color after Cycle 3
HALSl 0.15% Phos I 0.08 % 6.9 AOA 0.04 %
HALSl 0.15% Phos I 0.08 % 2.4 HAA 0.04 %
HALS 4 0.30 % Phos I 0.10% 2.7 AOA 0.05 %
HALS 4 0.30 % Phos I 0.05 % 1.2 HAA 0.05 %
HALS 5 0.30 % Phos I 0.10% 3.2 AOA 0.05 %
HALS 5 0.30 % Phos I 0.05 % 1.0 HAA 0.05 %
HALS 6 0.30 % Phos I 0.10% 2.1 AOA 0.05 %
HALS 6 0.30 % Phos I 0.05 % 1.0 HAA 0.05 %
HALS 7 0.30 % Phos I 0.10% 2.2 AOA 0.05 %
HALS 7 0.30 % Phos I 0.05 % 1.0 HAA 0.05 % Table 24:
Stabilizer Amount Delta E Color after Cycle 3
HALS l 0.15 % Phos in 0.08 % 5.6 AO A 0.04 %
HALS l 0.15 % Phos HI 0.08 % 3.8 HA A 0.04 %
Table 25:
Stabilizer Amount Delta E Color after Cycle 3
HALS l 0.15 % Phos IV 0.08 % 4.8 AO A 0.04 %
HALS l 0.15 % Phos IV 0.08 % 2.3 HA A 0.04 %
Inspection of the data given above shows that the instant formulations containing other se¬ lected hindered amines, other phosphites and hydroxylamines provide excellent gas fade resistance and color stability to polypropylene far superior to the stabilizer systems contai¬ ning a phenolic antioxidant.
Example 7: Gas Fade Resistance or Color Stability of Polypropylene Fiber
Following the procedure of Example 6, the gas fade resistance or color stability of poly¬ propylene fiber is measured when said fiber is protected by a binary system of stabilizers comprising a hindered amine and a hydroxylamine without the presence of any phosphite compared to fiber with additionally contains a phenolic antioxidant The test data are given in Tables 26, 27 and 28 below. Low Delta E values indicate less color and better sta¬ bilization. Table 26:
Stabilizer Amount Delta E Color after Cycle 3
HALSl 0.05 % Phos I 0.10% 4.7 AOA 0.05 %
HALSl 0.05 % HAA 0.10 % 1.0
HALSl 0.05 % HAA 0.05 % 1.2
Table 27:
Stabilizer Amount Delta E Color after Cycle 3
HALS 2 0.05 % Phos I 0.10% 4.1 AOA 0.05 %
HALS 2 0.05 % HAA 0.10% 0.9
HALS 2 0.05 % HAA 0.05 % 0.9
Table 28:
Stabilizer Amount Delta E Color after Cycle 3
HALS 3 0.05 % Phos I 0.10% 4.4 AOA 0.05 %
HALS 3 0.05 % HAA 0.10% 1.0
HALS 3 0.05 % HAA 0.05 % 0.9
Inspection of the data given above shows that the instant binary formulations containing selected hindered amines and hydroxylamines provide excellent gas fade resistance and color stability to polypropylene far superior to the stabilizer systems containing a phenolic antioxidant.
Example 8: Process Stabilization of Polypropylene Fiber
Melt flow differences resulting from insufficient processing stability are quite evident when toe polypropylene is spun under severe processing conditions. This is particularly evident when polypropylene is spun at 302°C. The lower the melt flow rates are the more effective is the process stabilization efficacy of the stabilizer system (see also example 1). The melt flow values of polypropylene spun at that temperature are shown in the Tables 29, 30 and 31 below.
Table 29:
Melt Row Rate
Stabilizer Amount Fiber Spun at 302°C
HALS 1 0.05 % 65
HALS l 0.05 % 34 Phos I 0.10 %
HALS l 0.05 % Phos I 0.10 % 16 AO A 0.05 %
HALS 1 0.05 % Phos I 0.05 % 18 HA A 0.05 %
HALS 1 0.05 % HA A 0.05 % 18 Table 30:
Melt Row Rate
Stabilizer Amount Fiber Spun at 302°C
HALS 2 0.05 % 56
HALS 2 0.05 % 24 Phos I 0.10 %
HALS 2 0.05 % Phos I 0.10 % 15 AO A 0.05 %
HALS 2 0.05 % Phos I 0.05 % 19 HA A 0.05 %
HALS 2 0.05 % 18 HA A 0.05 %
Table 31:
Melt Row Rate
Stabilizer Amount Fiber Spun at 302°C
HALS 3 0.05 % 28
HALS 3 0.05 % 31 Phos I 0.10 %
HALS 3 0.05 % Phos I 0.10 % 16 AO A 0.05 %
HALS 3 0.05 % Phos I 0.05 % 17 HA A 0.05 %
HALS 3 0.05 % 17 HA A 0.05 %
The data in Tables 29, 30 and 31 clearly show that in a conventional stabilizer system a combination of phenolic antioxidant, hindered amine and phosphite provide good processing stabUity. The removal of the phenolic antioxidant results in a significant loss in process stabilization. However, the substitution of a hydroxylamine in place of the phenolic antioxidant yields process stabilization fully comparable to that provided by the phenolic antioxidant-phosphite system both in the presence or absence of the phosphite component. Thus the binary stabilizer system of hindered amine plus hydroxylamine provides excellent thermal process stabilization to the polypropylene fiber.

Claims

WHAT IS CLAIMED IS:
1. A stabilized polypropylene fiber, free or essentially free of any phenolic antioxidant, and having enhanced light stability, enhanced long term heat stability and enhanced gas fade resistance, which fiber is stabilized by a mixture of
a) a hindered amine selected from the group consisting of
the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl- piperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine; toe polycondensation product of l-(2-hydroxyetoyl)-2,2,6,6-tetramethyl-4-hydroxy- piperidine and succinic acid;
N,N' ,N" ,N' "-tefrakis[4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino)-s- triazin-2-yl] -1,10-diamino-4,7-diazadecane ; the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetrametoyl- piperidine) and 2,4-dichloro-6-mo holino-s-triazine; poly[metoyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane; bis(2,2,6,6-teframetoylpiperidin-4-yl) cyclohexylenedioxydimethylmalonate; l,3,5-tris{N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)ethyl]amino-s- triazine; the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl- piperidine) and 2,4-dichloro-6-cyclohexylamino-s-triazine; and poly{N-[4,6-bis(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)amino)-s-triazin-2-yl]- l,4,7-triazanonane}- o-N"-[4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino)-s- triazin-2-yl]amine;
b) a phosphite selected from the group consisting of
tris(2,4-di-tert-butylphenyl) phosphite;
3,9-di(2,4-di-tert-butylphenyl)-2,4,8,10-tetraoxa-3,9-diphospha[5.5]undecane; 2,2',2"-nitrilo-tris[ethyl (3,3' ,5,5'-tetra-tert-butyl- 1 , 1 '-biphenyl-2,2'-diyl) phosphite] ; ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite; and tetrakis(2,4-di-tert-butylphenyl)-4,4'-bis(diphenylene)phosphonite; and
c) a hydroxylamine selected from the group consisting of N,N-dioctadecylhydroxylamine ;
N,N-dialkylhydroxylamine of the formula TjT2NOH where Tj^ and T2 are the alkyl mixture found in hydrogenated tallow amine; and the N,N-dialkylhydroxylamine product made by the direct oxidation of N,N-di(hydro- genated tallow)amine by toe process of US-A-5 013 510 or US-A-4 898 901;
wherein the weight ratio of components (a):(b):(c) is from 1:1:1 to 100:2:1.
2. A stabilized fiber according to claim 1 wherein component (a) is selected from the group consisting of
toe polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetrametoyl- piperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine; toe polycondensation product of l-(2-hydroxyetoyl)-2,2,6,6-tetramethyl-4-hydroxy- piperidine and succinic acid;
N,N' ,N" ,N' "-tetrakis[4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino)-s- triazin-2-yl]-l,10-diamino-4,7-diazadecane; the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetrametoyl- piperidine) and 2,4-dichloro-6-morpholino-s-triazine; poly[metoyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane; bis(2,2,6,6-teframetoylpiperidin-4-yl) cyclohexylenedioxydimethylmalonate; and l,3,5-tris{N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)ethyl]amino-s- triazine.
3. A stabilized fiber according to claim 1 wherein component (b) is selected from the group consisting of
tris(2,4-di-tert-butylphenyl) phosphite;
3,9-di(2,4-di-tert-butylphenyl)-2,4,8,10-tetraoxa-3,9-diphospha[5.5]undecane;
2,2',2"-nitrilo-tris[ethyl (3,3',5,5'-tetra-tert-butyM,l'-biphenyl-2,2'-diyl) phosphite]; and ethyl bis(2,4-di-tert-butyl-6-metoylphenyl) phosphite.
4. A stabilized fiber according to claim 1 wherein component (c) is the N,N-dialkyl- hydroxylamine product made by the direct oxidation of N,N-di(hydrogenated tallow)- amine by the process of US-A-5 013 510 or US-A-4898 901.
5. A stabilized fiber according to claim 1 wherein toe weight ratio of components (a):(b):(c) is from 10:1:1 to 10:2:1.
6. A stabilized fiber according to claim 1 wherein the amount of the mixture of stabilizers is from 0.05 to 5 % by weight based on the weight of toe fiber.
7. A method for enhancing gas fade resistance and reducing color formation in stabilized polypropylene fiber, witoout toe loss of any otoer stabilization property, by incorporating therein a mixture of stabilizers according to claim 1.
8. A metood for enhancing the resistance to degradation of polypropylene fiber, due to exposure to UV radiation over that which can be achieved by toe use of conventional sta¬ bilizers alone, by incorporating therein a mixture of stabilizers according to claim 1.
9. A metood for enhancing the thermal stability of polypropylene fiber, over that which can be achieved by the use of conventional stabilizers alone, by incorporating therein a mixture of stabilizers according to claim 1.
10. A stabilized polypropylene fiber, free or essentially free of any phenolic antioxidant, and having enhanced light stability, enhanced long term heat stability and enhanced gas fade resistance, which fiber is stabilized by a mixture of
I) a hindered amine selected from the group consisting of
the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl- piperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine; toe polycondensation product of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxy- piperidine and succinic acid;
N,N' ,N" ,N' "-tetralds[4,6-bis(butyl-(2,2,6,6-teframetoylpiperidin-4-yl)amino)-s- triazin-2-yl] -1,10-diamino-4,7-diazadecane ; the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetrametoyl- piperidine) and 2,4-dichloro-6-morpholino-s-triazine; poly[metoyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane; bis(2,2,6,6-tetramethylpiperidin-4-yl) cyclohexylenedioxydimethylmalonate;
1 ,3,5-tris { N-cyclohexyl-N-[2-(2,2,6,6-tetrametoylpiperazin-3-on-4-yl)ethyl]amino- s-triazine; and the polycondensation product of 4,4'-hexametoylene-bis(amino-2,2,6,6-tetramethyl- piperidine) and 2,4-dichloro-6-cyclohexylamino-s-triazine; and
π) a hydroxylamine selected from the group consisting of
N,N-dioctadecylhydroxylamine ;
N,N-dialkylhydroxylamine of the formula T^NOH where T2 and T2 are the alkyl mixture found in hydrogenated tallow amine; and the N,N-dialkylhydroxylamine product made by the direct oxidation of N,N-di(hy- drogenated tallow)amine by the process of US-A-5 013 510 or US-A-4 898 901;
wherein the weight ratio of components (I):(II) is from 100:1 to 1:2.
11. A stabilized fiber according to claim 10 wherein component (I) is selected from the group consisting of
the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl- piperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine; toe polycondensation product of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxy- piperidine and succinic acid; and
N,N' ,N" ,N' "-tetralris[4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino)-s- triazin-2-yl] -1,10-diamino-4,7-diazadecane.
12. A stabilized fiber according to claim 10 wherein component (II) is the N,N-diallcyl- hydroxylamine product made by the direct oxidation of N,N-di(hydrogenated tallow)- amine by the process of US-A-5 013 510 or US-A-4898 901.
13. A stabilized fiber according to claim 10 wherein the weight ratio of components (I):(π) is from 10:1 to 1:1.
14. A stabilized fiber according to claim 10 wherein the amount of toe mixture of stabi¬ lizers is from 0.05 to 5 % by weight based on the weight of the fiber.
15. A metood for enhancing gas fade resistance and reducing color formation in stabilized polypropylene fiber, witoout toe loss of any other stabilization property, by incorporating therein a mixture of stabilizers according to claim 10.
16. A method for enhancing the resistance to degradation of polypropylene fiber, due to exposure to UV radiation over toat which can be achieved by the use of conventional sta¬ bilizers alone, by incoφorating therein a mixture of stabilizers according to claim 10.
PCT/IB1994/000056 1993-04-15 1994-04-06 Low color processing, heat and light stabilizer system for polypropylene fiber WO1994024344A1 (en)

Priority Applications (14)

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DE4492361A DE4492361C2 (en) 1993-04-15 1994-04-06 Low-color heat and light stabilizer system for polypropylene fiber
SK1272-95A SK284817B6 (en) 1993-04-15 1994-04-06 Stabilized polypropylene fibre and increasing method of resistance and heat stability of polypropylene fibre
JP52295194A JP3424080B2 (en) 1993-04-15 1994-04-06 Low color processing, heat and light stabilizer system for polypropylene fibers
AU62632/94A AU6263294A (en) 1993-04-15 1994-04-06 Low color processing, heat and light stabilizer system for polypropylene fiber
KR1019950704499A KR100282620B1 (en) 1993-04-15 1994-04-06 Low color forming, thermal and light stabilizer systems for polypropylene fibers
DE4492361T DE4492361T1 (en) 1993-04-15 1994-04-06 Low-color heat and light stabilizer system for polypropylene fiber
BR9406876A BR9406876A (en) 1993-04-15 1994-04-06 Light and heat stabilized system in low color processing for polypropylene fiber
CA002160574A CA2160574C (en) 1993-04-15 1994-04-06 Low color processing, heat and light stabilizer system for polypropylene fiber
NL9420023A NL9420023A (en) 1993-04-15 1994-04-06 Stabilization system for polypropylene fibers against discoloration during processing and against discoloration by heat and light.
RU95120604A RU2126065C1 (en) 1993-04-15 1994-04-06 Light and heat-stabilizing mixture for polypropylene fiber without significant effect on color change
GB9520527A GB2292944B (en) 1993-04-15 1994-04-06 Low color processing, heat and light stabilizer system for polypropylene fiber
NO953932A NO309683B1 (en) 1993-04-15 1995-10-03 Low-color machining, heat and light stabilizer system for polypropylene fiber, and use of the same
DK199501109A DK175151B1 (en) 1993-04-15 1995-10-04 Stabilized polypropylene fibers, as well as methods for increasing gas bleach resistance and reducing color formation, increasing resistance to degradation due to exposure to UV radiation and increasing thermal stability ....
HK98104631A HK1005489A1 (en) 1993-04-15 1998-05-28 Low color processing heat and light stabilizer system for polypropylene fiber

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CA (1) CA2160574C (en)
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EP0880610A1 (en) 1996-02-12 1998-12-02 Fibervisions A/S Particle-containing fibres
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WO1999064507A1 (en) * 1998-06-12 1999-12-16 Montell North America Inc. Olefin polymer composition having low smoke generation and fiber, film and fabric prepared therefrom
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EP0710677A3 (en) * 1994-11-03 1998-02-04 Ciba SC Holding AG Process for producing stabilized olefin polymers
EP0710677A2 (en) * 1994-11-03 1996-05-08 Ciba-Geigy Ag Process for producing stabilized olefin polymers
US6020406A (en) * 1995-02-10 2000-02-01 Ciba Specialty Chemicals Corporation Synergistic stabilizer mixture
US6365651B1 (en) 1995-02-10 2002-04-02 Ciba Specialty Chemicals Corporation Synergistic stabilizer mixture
EP0880610A1 (en) 1996-02-12 1998-12-02 Fibervisions A/S Particle-containing fibres
KR100227221B1 (en) * 1997-04-01 1999-11-01 이정국 A polypropylene resin fiber composition having improved water-resistance and the textile using their fibers
EP0875530A1 (en) * 1997-05-02 1998-11-04 Montell North America Inc. Olefin polymer composition having low smoke generation and fiber and film prepared therefrom
US5834541A (en) * 1997-05-02 1998-11-10 Montell North America Inc. Olefin polymer composition having low smoke generation and fiber and film prepared therefrom
AU733943B2 (en) * 1997-05-02 2001-05-31 Montell North America Inc. Olefin polymer composition having low smoke generation and fiber and film prepared therefrom
EP0924251A1 (en) * 1997-12-18 1999-06-23 Montell North America Inc. Ductile, gamma radiation resistant polyolefin composition and articles produced therefrom
US5994436A (en) * 1997-12-18 1999-11-30 Montell North America Inc. Ductile gamma radiation resistant polyolefin composition and articles produced therefrom
US6172153B1 (en) 1998-06-12 2001-01-09 Montell North America Inc. Olefin polymer composition having low smoke generation and fiber, film and fabric prepared therefrom
WO1999064507A1 (en) * 1998-06-12 1999-12-16 Montell North America Inc. Olefin polymer composition having low smoke generation and fiber, film and fabric prepared therefrom
WO2000012605A1 (en) * 1998-08-26 2000-03-09 Union Carbide Chemicals & Plastics Technology Corporation Novel polypropylene compositions
BE1013624A5 (en) * 1999-03-01 2002-05-07 Ciba Sc Holding Ag Method for producing hollow articles polyolefin.
NL1014465C2 (en) * 1999-03-01 2002-01-29 Ciba Sc Holding Ag Stabilizer combination for the rotomolding process.
FR2791063A1 (en) * 1999-03-01 2000-09-22 Ciba Sc Holding Ag METHOD FOR THE PRODUCTION OF POLYOLEFIN HOLLOW ARTICLES IN THE PRESENCE OF PHOSPHITES AND/OR PHOSPHONITES, STERICALLY HINDRED AMINES AND HYDROXYLAMINES AND/OR AMINE OXIDES AS STABILIZERS
ES2170639A1 (en) * 1999-03-01 2002-08-01 Ciba Sc Holding Ag Stabilizer combination for the rotomolding process
DE10009416B4 (en) * 1999-03-01 2014-10-30 Ciba Holding Inc. Use of a stabilizer combination for the rotational molding process and process for the preparation of polyolefin hollow articles with the addition of the stabilizer combination
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WO2020239962A1 (en) 2019-05-30 2020-12-03 SI Group Switzerland (Chaa) Gmbh Antidegradant blend
GB2584305B (en) * 2019-05-30 2022-07-13 Si Group Switzerland Chaa Gmbh Antidegradant blend
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CA2160574C (en) 2004-02-03
GB9520527D0 (en) 1995-12-13
KR100282620B1 (en) 2001-02-15
CA2160574A1 (en) 1994-10-27
DE4492361T1 (en) 1997-08-21
AU6263294A (en) 1994-11-08
GB2292944A (en) 1996-03-13
HK1005489A1 (en) 1999-01-08
NO953932L (en) 1995-10-03
NO953932D0 (en) 1995-10-03
NO309683B1 (en) 2001-03-12
CN1051340C (en) 2000-04-12
DK110995A (en) 1995-10-04
AT405412B (en) 1999-08-25

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