CA2160574C - 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 PDFInfo
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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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
~~so~7~
_1_ 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 phosphonites and N,N-diallcylhydroxylamines, 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.
_7_ 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-4 360 617 have also achieved great commercial success as stabilizers.
N,N-Dialkylhydroxylamines also are known in the art as seen in US-A-4 590 231, US-A-4 782 105, US-A-4 876 300 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-4 876 300.
Although US-A-4 876 300 teaches generically that N,N-dialkylhydroxylamines 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-bilized 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-4 876 300.
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;
_1_ 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 phosphonites and N,N-diallcylhydroxylamines, 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.
_7_ 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-4 360 617 have also achieved great commercial success as stabilizers.
N,N-Dialkylhydroxylamines also are known in the art as seen in US-A-4 590 231, US-A-4 782 105, US-A-4 876 300 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-4 876 300.
Although US-A-4 876 300 teaches generically that N,N-dialkylhydroxylamines 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-bilized 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-4 876 300.
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 mquisites 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-tent-octylamino-s-triaxine;
the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4.-hydroxy-piperidine and succinic acid;
N,N' ,N" ,N' "-tetralas[4,6-bas(butyl-(2,2,6,6-tetramethylpipeiidin-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-b-moipholino-s-triazine;
poly[methyl 3-{2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane;
bas(2,2,6,6-tetramethylpiperidin-4-yl) cyclohexylenedioxydimethylmalonate;
1,3,5-tris { N-cyclohexyl-N-[2-(2,2,6,b-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-bas(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)amino)-s-triazba-2-yl]-1,4,7-triazanonane }-tn-N"-[4,6-bas(butyl-(2,2,6,6-tett~methylpiperidin-4.-yl)amino)-s-triazin-2-yl]amine;
b) a phosphate or phosphonite selected from the group consisting of tris(2,4-di-tert-butylphenyl) phosphate;
3,9-di(2,4-di-tert-butylphenyl)-2,4,8,10-tetraoxa-3,9-diphospha[S.S] undecane;
2,2',2"-nittilo-tris[ethyl (3,3',S,S'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphate];
ethyl bas(2,4-di-tert-butyl-6-methylphenyl) phosphate; 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 TI and TZ are the alkyl mixture found in hydrogenated tallow amine; and the N,N dialkylhydroxylamine product made by the direct oxidation of N,N-di(liydro-genated tallow)amine ;
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; aad most preferably 6:1:1 to 6:2:1.
T'he effective amount of the mixture of stabilizers is for example 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-t~aane;
the polycondensation product of 1-(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-tetramethylpiperidin-4.-yi)amino)-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane;
the polycondensation product of 4,4'-hezamethylene-bis(arnino-2,2,6,6-tetramethyl-piperidine) and 2,4-dichloro-6-morpholino-s-triazine;
poly[methyl 3-(2,2,6,6-tetcamethylpiperidin-4.-yloxy)propyl]siloxane;
bis(2,2,6,6-tetramethylpiperidin-4-yi) cyclohezylenedioxydimethylmalonate; and 1,3,5-Iris{N-cyclohexyl-N [2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl~thyl]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-butylpheny1~2,4,8,10-tetraoxa-3,9-diphospha[5.5] undecane;
2,2',2"-nittilo-tiffs[ethyl (3,3',S,S'-tetra-ten-butyl-1,1'-biphenyl-2,2'-diyl) phosphite];
and 29276-67? ~ 021.60574 2001-04-23 ethyl bis(2,4-di-cert butyl-6-methylphenyl) phosphite.
Stabilized polypropylene fiber which are particularly preferned are those where the com-;-- poneat (c) is the N,N-dialkyihYdroxY~ P~nct made by the direct oacidation of N,N-di(hydrogenated tallow)amine .
Additionally, the instant invention also pertains to a binary stab~izer System where the stn-b~i~ed polypropylene fiber, free or essentially free of any phenolic antioxidant, and having enhanced light stability, enhanced song term heat stability and.enhanced gas fade resistance, which fiber is stabilized by a miztare of I) a hindered amine selected from the group consisting of the polycondensation product of 4,4'-hexamethylene-his (amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine;
the polycondensation product of 1-(2-hydro~cyethyl)-2,2,6,6-teaamethyl-4-hydrozy piperidine and succinic acid;
N,N' ,N",N'"-oetralds[4,6-his(butyl-(2,2,6,6-tetramethyipiperidin-4-yi)amino)-s_ t<i,a~in-2-yl]-1,10-diamino-4,7 ;
the polycondensation product of 4,4'-heaamethylene-bis(amino-2,2,6,6-tetramethyl-piperidine) and 2,4-dichloro-6-morpholino-s-ttia~i~ne;
posy[methyl 3-(2,2.6,6-tetramethylpiperidin-4-ylozy)ProPYi]siloxane;
his(2,2,6,6-tetramethylpiperidin-4-yl) cyciohezylenedioxydimethylmalonate;
1,3,5-tds{N-cyclohe~rl-N-{2-(2,2,6,6-tetramethylniperazin 3-on-4-yl~ethyl]amino-s-t<iaane; and the poiycondensation product of 4,4'-hexamethyiene-bis(amino-2,2,6,6-tetramethyi piperidine) and 2,4-~iichloro-6-cycloheicyiamino-s-triazine; and In a hydro~cylamine selected from the group consisting of the N,N-dialkylhydroxylamine product made by the direct oxidation of N,N-di(hydrogenated tallow)amine;
wherein the weight ratio of components (I):(II) is from 100:1 to 1:2;
preferably 10:1 to 1:l; and most preferably S: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 polycondensadon product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl-piperidine) and 2,4-dichloro-6-tent-octylamino-s-triazine;
the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid; and N,N',N",N"'-tetrakis[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-S 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 °!o 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°ro by weight of phenolic antioxidant used in the working examples of US-A-4 876 300. 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 °k 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 ~1605'~4 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-4 782 105;
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 WO 94/24344 PCTlIB94/00056 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 purpose 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 - 1,3,5-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 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid;
DIALS 3 - N,N',N",N"'-tetrakis[4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl) amino)-s-triazin-2-yl]-1,10-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 - poly[methyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane;
HALS 6 - bis(2,2,6,6-tetramethylpiperidin-4-yl) cyclohexylenedioxydimethyl-malonate;
HALS 7 - 1,3,5-Iris{N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)-ethyl] amino-s-triazine;
Phos I - tris(2,4-di-tert-butylphenyl) phosphite;
Phos II - 3,9-di(2,4-di-tert-butylphenyl)-2,4,8,10-tetraoxa-3,9-diphospha[5.5]unde-cane;
Phos III - 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-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 °lo 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 WO 94/24344 2 ~ 6 0 5 7 4 PCT/IB94100056 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 A
Stabilizer mount Pellets Fiber HALS 1 0.30 Phos I 0.09 % 15.4 20.7 HA A 0.01 %
HALS 1 0.30 %
Phos I 0.05 % 14.9 19.6 HA A 0.05 %
HALS 1 0.05 %
Phos I 0.09 % 13.6 17.7 HA A 0.01 %
HALS 1 0.05 Phos I 0.05 % 13.6 18.8 HA A 0.05 %
AO A 0.05 HALS 1 0.05 % 14.3 19 Phos I 0.05 % .
HA A 0.05 %
Table 2:
elt Flow Rate bili A
S
ta mount zer Pellets Fiber HALS 2 0.30 %
Phos I 0.09 % 13.7 18.6 HA A 0.01 %
HALS 2 0.30 %
Phos I 0.05 % 13.8 18.3 HA A 0.05 %
HALS 2 0.05 %
Phos I 0.09 % 13.4 17.8 HA A 0.01 %
HALS 2 0.05 %
Phos I 0.05 % 14.4 18.7 HA A 0.05 %
AO A 0.05 HALS 2 0.05 % 12.9 18.1 Phos I 0.05 %
HA A 0.05 Table 3:
i A Melt Flow Rate lizer mount Stab Pellets Fiber HALS 3 0.30 %
Phos I 0.09 % 13.3 19.3 HA A 0.01 %
HALS 3 0.30 %
Phos I 0.05 % 14.2 17.5 HA A 0.05 %
HALS 3 0.05 %
Phos I 0.09 % 14.3 18.6 HA A 0.01 %
HALS 3 0.05 %
Phos I 0.05 % 13.7 18.4 HA A 0.05 AO A 0.05 %
HALS 3 0.05 % 12.8 17.5 Phos I 0.05 %
HA A 0.05 %
Table 4:
Melt Flow Rate StabilizerAmount Pellets Fiber HALS 2 0.05 %
Phos II 0.05 % 12.7 16.9 HA A 0.05 %
AO A 0.05 %a HALS 2 0.05 % 12 16.2 Phos II 0.05 .
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.
21GQ~~,~
Table S:
Melt Flow Rate Stabilizer Amount Fiber Spun Fiber Spun at 274C at 302C
Phos I 0.15 % 14.6 26.9 Phos I 0.10 % 13 15.5 AO A 0.05 % .
Phos I 0.05 % 12.7 16 AO A 0.05 % .
Phos I 0.10 % 13.5 16 HA A 0.05 % .
HALS 2 0.05 % 15 31 Phos I 0.10 . .
HALS 2 0.05 %
Phos I 0.10 % 14.3 16.3 AO A 0.05 %
HALS 2 0.05 Phos I 0.05 % 13.7 17.4 HA A 0.05 HALS 2 0.05 %
Phos I 0.10 % 13.6 16.1 HA A 0.05 %
Table 6:
Melt Flow Rate Stabilizer Amount Fiber Spun Fiber Spun at 274C at 302C
Phos II 0.15 % 13.7 20.1 Phos II 0.10 % 13.0 16.5 AO A 0.05 %
HALS 2 0.05 % 15.2 22.2 Phos II 0.10 HALS 2 0.05 %
Phos II 0.10 % 12.2 15.5 AO A 0.05 HALS 2 0.05 %
Phos II 0.05 % 12.4 15.5 HA A 0.05 %
HALS 2 0.05 %
Phos II 0.10 % 12.7 15.6 HA A 0.05 %
WO 94/24344 .
PCTlIB94100056 Table 7:
Melt Flow Rate Stabilizer Aifridu~.t~ Fiber Spun Fiber Spun at 274C at 302C
Phos I 0.15 % 14.6 26.9 Phos I 0.10 % 13.3 15.5 AO A 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 AO A 0.05 %
HALS 3 0.05 %
Phos I 0.05 % 12.4 16.9 HA A 0.05 %
HALS 3 0.05 Phos I 0.10 % 12.9 16.7 HA A 0.05 %
Table 8:
Melt Flow Rate Stabilizer Amount Fiber Spun Fiber Spun at 274C at 302C
Phos II 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 II 0.10 %
HALS 3 0.05 %
Phos II 0.05 % 13.1 14.9 HA A 0.05 %
HALS 3 0.05 Phos II 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 S, 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 teen 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-WO 94/24344 ~ ~ PCT/IB94/00056 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:
StabilizerAmount Days to Failure in the WeatherOmeter HALS 1 0.30 %
Phos I 0.09 % 34 HA A 0.01 %
HALS 1 0.30 %
Phos I 0.05 % 38 HA A 0.05 HALS 1 0.30 %
AO A 0.05 % 38 Phos I 0.05 %
HA A 0.05 %
HALS 1 0.30 %
AO A 0.05 % 28 Phos I 0.10 %
Table 10:
StabilizerAmount 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:
Days to Failure in StabilizerAmount the WeatherOmeter HALS 3 0.30 %
Phos I 0.09 % 38 HA A 0.01 %
HALS 3 0.30 %
Phos I 0.05 % 37 Hp A 0.05 Table 12:
Days to Failure in Stabilizer Amount the WeatherOmeter HALS 2 0.05 %
Phos II 0.05 % 9 HA A 0.05 %
Ex~le 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:
Days to Failure Stabilizer Amount at 120C
HALS 1 0.30 %
Phos I 0.09 % 65 HA A 0.01 HALS 1 0.30 %
Phos I 0.05 % 61 HA A 0.05 %
~I~~~'~4 Table 14:
StabilizerAmount Days to Failure at 120C
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 StabilizerAmount at 120C
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 mixtum 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, "Colorfastness 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 StabilizerAmount HALS 1 0.30 %
Phos I 0.09 % 2.4 2.8 HA A 0.01 %
HALS 1 0.30 %
Phos I 0.05 % 2.3 2.9 HA A 0.05 %
HALS 1 0.30 %
AO A 0.05 % 5.7 6.7 Phos I 0.09 %
HA A 0.01 %
HALS 1 0.30 %
AO A 0.05 % 4 6.1 Phos I 0.05 % .
HA A 0.05 %
Table 17:
Delta E
Color after Cycle A
Stabilizermount HALS 1 0.05 %
Phos I 0.09 % 1.9 1.5 HA A 0.01 %
HALS 1 0.05 %
Phos I 0.05 % 1.8 1.9 HA A 0.05 %
HALS 1 0.05 %
AO A 0.05 % 3,g 5.2 Phos I 0.09 %
HA A 0.01 %
HALS 1 0.05 %
AO A 0.05 %
2 5.0 Phos I 0.05 % .
HA A 0.05 %
Table 18:
Delta E Color after Cycle St A
bili t zer moun a HALS 2 0.30 Phos I 0.09 % 1.6 1.5 HA A 0.01 %
HALS 2 0.30 %
Phos I 0.05 % 1.5 1.9 HA A 0.05 %
HALS 2 0.30 %
AO A 0.05 % 3 5 Phos I 0.09 % . .
HA A 0.01 %
HALS 2 0.30 AO A 0.05 % 1 3.7 Phos I 0.05 % .
HA A 0.05 %
Table 19:
Delta E
Color after Cycle bili A
S t zer moun ta HALS 2 0.05 %
Phos I 0.09 % 1.6 1.5 HA A 0.01 HALS 2 0.05 %
Phos I 0.05 % 1.0 1.3 HA A 0.05 %
HALS 2 0.05 %
AO A 0.05 % 3,g 4.9 Phos I 0.09 %
HA A 0.01 %
HALS 2 0.05 %
AO A 0.05 %
2 3.9 Phos I 0.05 % .
HA A 0.05 %
Table 20:
Delta E
A Color after Cycle Stabilizer mount HALS 3 0.30 %
Phos I 0.09 % 2.4 2.3 HA A 0.01 %
HALS 3 0.30 Phos I 0.05 % 1.7 1.9 HA A 0.05 HALS 3 0.30 %
AO A 0.05 % 4.g 6.7 Phos I 0.09 %
HA A 0.01 %
HALS 3 0.30 %
AO A 0.05 %
1 5.3 Phos I 0.05 % .
HA A 0.05 %
Table 21:
Delta E
A Color after Cycle Stabilizer mount HALS 3 0.05 %
Phos I 0.09 % 1.9 1.6 HA A 0.01 %
HALS 3 0.05 %
Phos I 0.05 % 1.2 1.3 HA A 0.05 %
HALS 3 0.05 %
AO A 0.05 % 4.0 5.3 Phos I 0.09 %
HA A 0.01 %
HALS 3 0.05 %
AO A 0.05 %
2 4.6 Phos I 0.05 % ~
HA A 0.05 %
WO 94124344 ~ PCT/IB94/00056 Table 22:
Delta E
Color after Cycle St nt bili A
o zer m a u 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 1 Phos II 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, "Colorfastness 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-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:
StabilizerAmount Delta E Color after Cycle 3 HALS 1 0.15 %
Phos I 0.08 % 6.9 AO A 0.04 HALS 1 0.15 %
Phos I 0.08 % 2.4 HA A 0.04 %
HALS 4 0.30 %
Phos I 0.10 %
AO A 0.05 HALS 4 0.30 %
Phos I 0.05 % 1.2 HA A 0.05 %
HALS 5 0.30 %
Phos I 0.10 % 3.2 AO A 0.05 %
HALS 5 0.30 %
Phos I 0.05 % 1.0 HA A 0.05 %
HALS 6 0.30 %
Phos I 0.10 % 2.1 AO A 0.05 %
HALS 6 0.30 %
Phos I 0.05 % 1.0 HA A 0.05 %
HALS 7 0.30 Phos I 0.10 % 2.2 AO A 0.05 %
HALS 7 0.30 %
Phos I 0.05 % 1.0 HA A 0.05 %
WO 94/24344 . PCT/IB94100056 Table 24:
StabilizerAmount Delta E Color after Cycle 3 HALS 1 0.15 Phos III 0.08 % 5.6 AO A 0.04 %
HALS 1 0.15 %
Phos III 0.08 % 3.8 HA A 0.04 %
Table 25:
StabilizerAmount Delta E Color after Cycle 3 HALS 1 0.15 %
Phos IV 0.08 % 4.8 AO A 0.04 %
HALS 1 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.
_26_ Table 26:
StabilizerAmount Delta E Color after Cycle 3 HALS 1 0.05 %
Phos I 0.10 % 4.7 AO A 0.05 %
HALS 1 0.05 %
HA A 0.10 % .
HALS 1 0.05 %
HAA 0.05% .
Table 27:
StabilizerAmount Delta E Color after Cycle 3 HALS 2 0.05 %
Phos I 0.10 % 4.1 AO A 0.05 %
HALS 2 0.05 HA A 0.10 % .
HALS 2 0.05 %
Hp A 0.05 % .
Table 28:
StabilizerAmount Delta E Color after Cycle 3 HALS 3 0.05 Phos I 0.10 % 4.4 AO A 0.05 %
HALS 3 0.05 %
HA A 0.10 % .
HALS 3 0.05 %
HA A 0.05 % .
Inspection of the data given above shows that the instant binary formulations containing msa5~4 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 the 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 Flow Rate Stabilizer Amount Fiber Spun at HALS 1 0.05 % 65 HALS 1 0.05 % 34 Phos I 0.10 %
HALS 1 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 % 1 g HA A 0.05 %
_28_ Table 30:
Melt Flow Rate Stabilizer Amount Fiber Spun at 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 Flow Rate Stabilizer Amount Fiber Spun at 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 %a Phos I 0.05 % 1~
HA A 0.05 %
HALS 3 0.05 % 1~
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 stability. 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 zisos~~
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.
and 3. Phosphites plus hindered amines lack adequate process stabilization.
The instant combination of stabilizers provide all of the required mquisites 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-tent-octylamino-s-triaxine;
the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4.-hydroxy-piperidine and succinic acid;
N,N' ,N" ,N' "-tetralas[4,6-bas(butyl-(2,2,6,6-tetramethylpipeiidin-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-b-moipholino-s-triazine;
poly[methyl 3-{2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane;
bas(2,2,6,6-tetramethylpiperidin-4-yl) cyclohexylenedioxydimethylmalonate;
1,3,5-tris { N-cyclohexyl-N-[2-(2,2,6,b-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-bas(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)amino)-s-triazba-2-yl]-1,4,7-triazanonane }-tn-N"-[4,6-bas(butyl-(2,2,6,6-tett~methylpiperidin-4.-yl)amino)-s-triazin-2-yl]amine;
b) a phosphate or phosphonite selected from the group consisting of tris(2,4-di-tert-butylphenyl) phosphate;
3,9-di(2,4-di-tert-butylphenyl)-2,4,8,10-tetraoxa-3,9-diphospha[S.S] undecane;
2,2',2"-nittilo-tris[ethyl (3,3',S,S'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphate];
ethyl bas(2,4-di-tert-butyl-6-methylphenyl) phosphate; 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 TI and TZ are the alkyl mixture found in hydrogenated tallow amine; and the N,N dialkylhydroxylamine product made by the direct oxidation of N,N-di(liydro-genated tallow)amine ;
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; aad most preferably 6:1:1 to 6:2:1.
T'he effective amount of the mixture of stabilizers is for example 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-t~aane;
the polycondensation product of 1-(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-tetramethylpiperidin-4.-yi)amino)-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane;
the polycondensation product of 4,4'-hezamethylene-bis(arnino-2,2,6,6-tetramethyl-piperidine) and 2,4-dichloro-6-morpholino-s-triazine;
poly[methyl 3-(2,2,6,6-tetcamethylpiperidin-4.-yloxy)propyl]siloxane;
bis(2,2,6,6-tetramethylpiperidin-4-yi) cyclohezylenedioxydimethylmalonate; and 1,3,5-Iris{N-cyclohexyl-N [2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl~thyl]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-butylpheny1~2,4,8,10-tetraoxa-3,9-diphospha[5.5] undecane;
2,2',2"-nittilo-tiffs[ethyl (3,3',S,S'-tetra-ten-butyl-1,1'-biphenyl-2,2'-diyl) phosphite];
and 29276-67? ~ 021.60574 2001-04-23 ethyl bis(2,4-di-cert butyl-6-methylphenyl) phosphite.
Stabilized polypropylene fiber which are particularly preferned are those where the com-;-- poneat (c) is the N,N-dialkyihYdroxY~ P~nct made by the direct oacidation of N,N-di(hydrogenated tallow)amine .
Additionally, the instant invention also pertains to a binary stab~izer System where the stn-b~i~ed polypropylene fiber, free or essentially free of any phenolic antioxidant, and having enhanced light stability, enhanced song term heat stability and.enhanced gas fade resistance, which fiber is stabilized by a miztare of I) a hindered amine selected from the group consisting of the polycondensation product of 4,4'-hexamethylene-his (amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine;
the polycondensation product of 1-(2-hydro~cyethyl)-2,2,6,6-teaamethyl-4-hydrozy piperidine and succinic acid;
N,N' ,N",N'"-oetralds[4,6-his(butyl-(2,2,6,6-tetramethyipiperidin-4-yi)amino)-s_ t<i,a~in-2-yl]-1,10-diamino-4,7 ;
the polycondensation product of 4,4'-heaamethylene-bis(amino-2,2,6,6-tetramethyl-piperidine) and 2,4-dichloro-6-morpholino-s-ttia~i~ne;
posy[methyl 3-(2,2.6,6-tetramethylpiperidin-4-ylozy)ProPYi]siloxane;
his(2,2,6,6-tetramethylpiperidin-4-yl) cyciohezylenedioxydimethylmalonate;
1,3,5-tds{N-cyclohe~rl-N-{2-(2,2,6,6-tetramethylniperazin 3-on-4-yl~ethyl]amino-s-t<iaane; and the poiycondensation product of 4,4'-hexamethyiene-bis(amino-2,2,6,6-tetramethyi piperidine) and 2,4-~iichloro-6-cycloheicyiamino-s-triazine; and In a hydro~cylamine selected from the group consisting of the N,N-dialkylhydroxylamine product made by the direct oxidation of N,N-di(hydrogenated tallow)amine;
wherein the weight ratio of components (I):(II) is from 100:1 to 1:2;
preferably 10:1 to 1:l; and most preferably S: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 polycondensadon product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethyl-piperidine) and 2,4-dichloro-6-tent-octylamino-s-triazine;
the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid; and N,N',N",N"'-tetrakis[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-S 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 °!o 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°ro by weight of phenolic antioxidant used in the working examples of US-A-4 876 300. 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 °k 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 ~1605'~4 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-4 782 105;
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 WO 94/24344 PCTlIB94/00056 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 purpose 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 - 1,3,5-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 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid;
DIALS 3 - N,N',N",N"'-tetrakis[4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl) amino)-s-triazin-2-yl]-1,10-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 - poly[methyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane;
HALS 6 - bis(2,2,6,6-tetramethylpiperidin-4-yl) cyclohexylenedioxydimethyl-malonate;
HALS 7 - 1,3,5-Iris{N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)-ethyl] amino-s-triazine;
Phos I - tris(2,4-di-tert-butylphenyl) phosphite;
Phos II - 3,9-di(2,4-di-tert-butylphenyl)-2,4,8,10-tetraoxa-3,9-diphospha[5.5]unde-cane;
Phos III - 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-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 °lo 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 WO 94/24344 2 ~ 6 0 5 7 4 PCT/IB94100056 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 A
Stabilizer mount Pellets Fiber HALS 1 0.30 Phos I 0.09 % 15.4 20.7 HA A 0.01 %
HALS 1 0.30 %
Phos I 0.05 % 14.9 19.6 HA A 0.05 %
HALS 1 0.05 %
Phos I 0.09 % 13.6 17.7 HA A 0.01 %
HALS 1 0.05 Phos I 0.05 % 13.6 18.8 HA A 0.05 %
AO A 0.05 HALS 1 0.05 % 14.3 19 Phos I 0.05 % .
HA A 0.05 %
Table 2:
elt Flow Rate bili A
S
ta mount zer Pellets Fiber HALS 2 0.30 %
Phos I 0.09 % 13.7 18.6 HA A 0.01 %
HALS 2 0.30 %
Phos I 0.05 % 13.8 18.3 HA A 0.05 %
HALS 2 0.05 %
Phos I 0.09 % 13.4 17.8 HA A 0.01 %
HALS 2 0.05 %
Phos I 0.05 % 14.4 18.7 HA A 0.05 %
AO A 0.05 HALS 2 0.05 % 12.9 18.1 Phos I 0.05 %
HA A 0.05 Table 3:
i A Melt Flow Rate lizer mount Stab Pellets Fiber HALS 3 0.30 %
Phos I 0.09 % 13.3 19.3 HA A 0.01 %
HALS 3 0.30 %
Phos I 0.05 % 14.2 17.5 HA A 0.05 %
HALS 3 0.05 %
Phos I 0.09 % 14.3 18.6 HA A 0.01 %
HALS 3 0.05 %
Phos I 0.05 % 13.7 18.4 HA A 0.05 AO A 0.05 %
HALS 3 0.05 % 12.8 17.5 Phos I 0.05 %
HA A 0.05 %
Table 4:
Melt Flow Rate StabilizerAmount Pellets Fiber HALS 2 0.05 %
Phos II 0.05 % 12.7 16.9 HA A 0.05 %
AO A 0.05 %a HALS 2 0.05 % 12 16.2 Phos II 0.05 .
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.
21GQ~~,~
Table S:
Melt Flow Rate Stabilizer Amount Fiber Spun Fiber Spun at 274C at 302C
Phos I 0.15 % 14.6 26.9 Phos I 0.10 % 13 15.5 AO A 0.05 % .
Phos I 0.05 % 12.7 16 AO A 0.05 % .
Phos I 0.10 % 13.5 16 HA A 0.05 % .
HALS 2 0.05 % 15 31 Phos I 0.10 . .
HALS 2 0.05 %
Phos I 0.10 % 14.3 16.3 AO A 0.05 %
HALS 2 0.05 Phos I 0.05 % 13.7 17.4 HA A 0.05 HALS 2 0.05 %
Phos I 0.10 % 13.6 16.1 HA A 0.05 %
Table 6:
Melt Flow Rate Stabilizer Amount Fiber Spun Fiber Spun at 274C at 302C
Phos II 0.15 % 13.7 20.1 Phos II 0.10 % 13.0 16.5 AO A 0.05 %
HALS 2 0.05 % 15.2 22.2 Phos II 0.10 HALS 2 0.05 %
Phos II 0.10 % 12.2 15.5 AO A 0.05 HALS 2 0.05 %
Phos II 0.05 % 12.4 15.5 HA A 0.05 %
HALS 2 0.05 %
Phos II 0.10 % 12.7 15.6 HA A 0.05 %
WO 94/24344 .
PCTlIB94100056 Table 7:
Melt Flow Rate Stabilizer Aifridu~.t~ Fiber Spun Fiber Spun at 274C at 302C
Phos I 0.15 % 14.6 26.9 Phos I 0.10 % 13.3 15.5 AO A 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 AO A 0.05 %
HALS 3 0.05 %
Phos I 0.05 % 12.4 16.9 HA A 0.05 %
HALS 3 0.05 Phos I 0.10 % 12.9 16.7 HA A 0.05 %
Table 8:
Melt Flow Rate Stabilizer Amount Fiber Spun Fiber Spun at 274C at 302C
Phos II 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 II 0.10 %
HALS 3 0.05 %
Phos II 0.05 % 13.1 14.9 HA A 0.05 %
HALS 3 0.05 Phos II 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 S, 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 teen 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-WO 94/24344 ~ ~ PCT/IB94/00056 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:
StabilizerAmount Days to Failure in the WeatherOmeter HALS 1 0.30 %
Phos I 0.09 % 34 HA A 0.01 %
HALS 1 0.30 %
Phos I 0.05 % 38 HA A 0.05 HALS 1 0.30 %
AO A 0.05 % 38 Phos I 0.05 %
HA A 0.05 %
HALS 1 0.30 %
AO A 0.05 % 28 Phos I 0.10 %
Table 10:
StabilizerAmount 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:
Days to Failure in StabilizerAmount the WeatherOmeter HALS 3 0.30 %
Phos I 0.09 % 38 HA A 0.01 %
HALS 3 0.30 %
Phos I 0.05 % 37 Hp A 0.05 Table 12:
Days to Failure in Stabilizer Amount the WeatherOmeter HALS 2 0.05 %
Phos II 0.05 % 9 HA A 0.05 %
Ex~le 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:
Days to Failure Stabilizer Amount at 120C
HALS 1 0.30 %
Phos I 0.09 % 65 HA A 0.01 HALS 1 0.30 %
Phos I 0.05 % 61 HA A 0.05 %
~I~~~'~4 Table 14:
StabilizerAmount Days to Failure at 120C
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 StabilizerAmount at 120C
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 mixtum 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, "Colorfastness 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 StabilizerAmount HALS 1 0.30 %
Phos I 0.09 % 2.4 2.8 HA A 0.01 %
HALS 1 0.30 %
Phos I 0.05 % 2.3 2.9 HA A 0.05 %
HALS 1 0.30 %
AO A 0.05 % 5.7 6.7 Phos I 0.09 %
HA A 0.01 %
HALS 1 0.30 %
AO A 0.05 % 4 6.1 Phos I 0.05 % .
HA A 0.05 %
Table 17:
Delta E
Color after Cycle A
Stabilizermount HALS 1 0.05 %
Phos I 0.09 % 1.9 1.5 HA A 0.01 %
HALS 1 0.05 %
Phos I 0.05 % 1.8 1.9 HA A 0.05 %
HALS 1 0.05 %
AO A 0.05 % 3,g 5.2 Phos I 0.09 %
HA A 0.01 %
HALS 1 0.05 %
AO A 0.05 %
2 5.0 Phos I 0.05 % .
HA A 0.05 %
Table 18:
Delta E Color after Cycle St A
bili t zer moun a HALS 2 0.30 Phos I 0.09 % 1.6 1.5 HA A 0.01 %
HALS 2 0.30 %
Phos I 0.05 % 1.5 1.9 HA A 0.05 %
HALS 2 0.30 %
AO A 0.05 % 3 5 Phos I 0.09 % . .
HA A 0.01 %
HALS 2 0.30 AO A 0.05 % 1 3.7 Phos I 0.05 % .
HA A 0.05 %
Table 19:
Delta E
Color after Cycle bili A
S t zer moun ta HALS 2 0.05 %
Phos I 0.09 % 1.6 1.5 HA A 0.01 HALS 2 0.05 %
Phos I 0.05 % 1.0 1.3 HA A 0.05 %
HALS 2 0.05 %
AO A 0.05 % 3,g 4.9 Phos I 0.09 %
HA A 0.01 %
HALS 2 0.05 %
AO A 0.05 %
2 3.9 Phos I 0.05 % .
HA A 0.05 %
Table 20:
Delta E
A Color after Cycle Stabilizer mount HALS 3 0.30 %
Phos I 0.09 % 2.4 2.3 HA A 0.01 %
HALS 3 0.30 Phos I 0.05 % 1.7 1.9 HA A 0.05 HALS 3 0.30 %
AO A 0.05 % 4.g 6.7 Phos I 0.09 %
HA A 0.01 %
HALS 3 0.30 %
AO A 0.05 %
1 5.3 Phos I 0.05 % .
HA A 0.05 %
Table 21:
Delta E
A Color after Cycle Stabilizer mount HALS 3 0.05 %
Phos I 0.09 % 1.9 1.6 HA A 0.01 %
HALS 3 0.05 %
Phos I 0.05 % 1.2 1.3 HA A 0.05 %
HALS 3 0.05 %
AO A 0.05 % 4.0 5.3 Phos I 0.09 %
HA A 0.01 %
HALS 3 0.05 %
AO A 0.05 %
2 4.6 Phos I 0.05 % ~
HA A 0.05 %
WO 94124344 ~ PCT/IB94/00056 Table 22:
Delta E
Color after Cycle St nt bili A
o zer m a u 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 1 Phos II 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, "Colorfastness 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-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:
StabilizerAmount Delta E Color after Cycle 3 HALS 1 0.15 %
Phos I 0.08 % 6.9 AO A 0.04 HALS 1 0.15 %
Phos I 0.08 % 2.4 HA A 0.04 %
HALS 4 0.30 %
Phos I 0.10 %
AO A 0.05 HALS 4 0.30 %
Phos I 0.05 % 1.2 HA A 0.05 %
HALS 5 0.30 %
Phos I 0.10 % 3.2 AO A 0.05 %
HALS 5 0.30 %
Phos I 0.05 % 1.0 HA A 0.05 %
HALS 6 0.30 %
Phos I 0.10 % 2.1 AO A 0.05 %
HALS 6 0.30 %
Phos I 0.05 % 1.0 HA A 0.05 %
HALS 7 0.30 Phos I 0.10 % 2.2 AO A 0.05 %
HALS 7 0.30 %
Phos I 0.05 % 1.0 HA A 0.05 %
WO 94/24344 . PCT/IB94100056 Table 24:
StabilizerAmount Delta E Color after Cycle 3 HALS 1 0.15 Phos III 0.08 % 5.6 AO A 0.04 %
HALS 1 0.15 %
Phos III 0.08 % 3.8 HA A 0.04 %
Table 25:
StabilizerAmount Delta E Color after Cycle 3 HALS 1 0.15 %
Phos IV 0.08 % 4.8 AO A 0.04 %
HALS 1 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.
_26_ Table 26:
StabilizerAmount Delta E Color after Cycle 3 HALS 1 0.05 %
Phos I 0.10 % 4.7 AO A 0.05 %
HALS 1 0.05 %
HA A 0.10 % .
HALS 1 0.05 %
HAA 0.05% .
Table 27:
StabilizerAmount Delta E Color after Cycle 3 HALS 2 0.05 %
Phos I 0.10 % 4.1 AO A 0.05 %
HALS 2 0.05 HA A 0.10 % .
HALS 2 0.05 %
Hp A 0.05 % .
Table 28:
StabilizerAmount Delta E Color after Cycle 3 HALS 3 0.05 Phos I 0.10 % 4.4 AO A 0.05 %
HALS 3 0.05 %
HA A 0.10 % .
HALS 3 0.05 %
HA A 0.05 % .
Inspection of the data given above shows that the instant binary formulations containing msa5~4 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 the 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 Flow Rate Stabilizer Amount Fiber Spun at HALS 1 0.05 % 65 HALS 1 0.05 % 34 Phos I 0.10 %
HALS 1 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 % 1 g HA A 0.05 %
_28_ Table 30:
Melt Flow Rate Stabilizer Amount Fiber Spun at 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 Flow Rate Stabilizer Amount Fiber Spun at 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 %a Phos I 0.05 % 1~
HA A 0.05 %
HALS 3 0.05 % 1~
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 stability. 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 zisos~~
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 (15)
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-tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine;
the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid;
N,N',N",N"'-tetrakis[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-tetramethylpiperidine) 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;
1,3,5-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-tetramethylpiperidine) and 2,4-dichloro-6-cyclohexylamino-s-triazine; and poly{N-[4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,4,7-triazanonane)-.omega.-N"-[4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino)-s-triazin-2 -yl]amine;
b) a phosphite or phosphonite 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 T1T2NOH where T1 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(hydrogenated tallow)amine;
wherein the weight ratio of components (a):(b):(c) is from 1:1:1 to 100:2:1.
the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid;
N,N',N",N"'-tetrakis[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-tetramethylpiperidine) 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;
1,3,5-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-tetramethylpiperidine) and 2,4-dichloro-6-cyclohexylamino-s-triazine; and poly{N-[4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,4,7-triazanonane)-.omega.-N"-[4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino)-s-triazin-2 -yl]amine;
b) a phosphite or phosphonite 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 T1T2NOH where T1 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(hydrogenated tallow)amine;
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 the polycondensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine;
the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid;
N,N',N",N"'-tetrakis[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-tetramethylpiperidine) 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 1,3,5-tris{N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)ethyl]amino-s-triazine.
the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid;
N,N',N",N"'-tetrakis[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-tetramethylpiperidine) 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 1,3,5-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 or 2 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-butyl-1,1'-biphenyl-2,2'-diyl)phosphite]; and ethyl bis(2,4-di-tert-butyl-6-methylphenyl)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]; and ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite.
4. A stabilized fiber according to any one of claims 1 to 3 wherein component (c) is the N,N-dialkylhydroxylamine product made by the direct oxidation of N,N-di(hydrogenated tallow) amine.
5. A stabilized fiber according to any one of claims 1 to 4 wherein the weight ratio of components (a):(b):(c) is from 10:1:1 to 10:2:1.
6.~A stabilized fiber according to any one of claims 1 to 5 wherein the amount of the mixture of stabilizers is from 0.05 to 5% by weight based on the weight of the fiber.
7. A method for enhancing gas fade resistance and reducing colour formation in stabilized polypropylene fiber, without the loss of any other stabilization property, by incorporating therein a mixture of stabilizers as defined in any one of claims 1 to 6.
8. 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 a mixture of stabilizers as defined in any one of claims 1 to 6.
9. A method 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 as defined in any one of claims 1 to 6.
10. A stabilized polypropylene fiber, free of 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-tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine;
the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid;
N,N',N",N"'-tetrakis[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-tetramethylpiperidine) 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;
1,3,5-tris(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-tetramethylpiperidine) and 2,4-dichloro-6-cyclohexylamino-s-triazine; and (II) the N,N-dialkylhydroxylamine product made by the direct oxidation of N,N-di(hydrogenated tallow)amine;
wherein the weight ratio of components (I):(II) is from 100:1 to 1:2.
the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid;
N,N',N",N"'-tetrakis[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-tetramethylpiperidine) 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;
1,3,5-tris(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-tetramethylpiperidine) and 2,4-dichloro-6-cyclohexylamino-s-triazine; and (II) the N,N-dialkylhydroxylamine product made by the direct oxidation of N,N-di(hydrogenated tallow)amine;
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-tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine;
the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; and N,N' ,N" ,N"'-tetrakis [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 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; and N,N' ,N" ,N"'-tetrakis [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 l0 or 11 wherein the weight ratio of components (I):(II) is from 10:1 to 1:1.
13. A stabilized fiber according to any one of claims 10 to 12 wherein the amount of the mixture of stabilizers is from 0.05 to 5% by weight based on the weight of the fiber.
14. A method for enhancing gas fade resistance and reducing colour formation in stabilized polypropylene fiber, without the loss of any other stabilization property, by incorporating therein a mixture of stabilizers as defined in any one of claims 10 to 13.
15. 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 a mixture of stabilizers as defined in any one of claims 10 to 13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US4808693A | 1993-04-15 | 1993-04-15 | |
| US08/048,086 | 1993-04-15 | ||
| PCT/IB1994/000056 WO1994024344A1 (en) | 1993-04-15 | 1994-04-06 | Low color processing, heat and light stabilizer system for polypropylene fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2160574A1 CA2160574A1 (en) | 1994-10-27 |
| CA2160574C true CA2160574C (en) | 2004-02-03 |
Family
ID=21952660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002160574A Expired - Lifetime CA2160574C (en) | 1993-04-15 | 1994-04-06 | Low color processing, heat and light stabilizer system for polypropylene fiber |
Country Status (20)
| Country | Link |
|---|---|
| JP (1) | JP3424080B2 (en) |
| KR (1) | KR100282620B1 (en) |
| CN (1) | CN1051340C (en) |
| AT (1) | AT405412B (en) |
| AU (1) | AU6263294A (en) |
| BE (1) | BE1006850A3 (en) |
| BR (1) | BR9406876A (en) |
| CA (1) | CA2160574C (en) |
| DE (2) | DE4492361C2 (en) |
| DK (1) | DK175151B1 (en) |
| FR (1) | FR2704009B1 (en) |
| GB (1) | GB2292944B (en) |
| HK (1) | HK1005489A1 (en) |
| IT (1) | IT1269313B (en) |
| NL (1) | NL9420023A (en) |
| NO (1) | NO309683B1 (en) |
| RU (1) | RU2126065C1 (en) |
| SK (1) | SK284817B6 (en) |
| TW (1) | TW268052B (en) |
| WO (1) | WO1994024344A1 (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2705679B1 (en) * | 1993-05-24 | 1998-07-10 | Sandoz Sa | New stabilizing compositions for polymeric materials, based on phosphonites or phosphites and a stabilizer against hydrolysis. |
| EP0710677A3 (en) * | 1994-11-03 | 1998-02-04 | Ciba SC Holding AG | Process for producing stabilized olefin polymers |
| TW401437B (en) | 1995-02-10 | 2000-08-11 | Ciba Sc Holding Ag | Synergistic stabilizer mixture |
| WO1997030199A1 (en) | 1996-02-12 | 1997-08-21 | Fibervisions A/S | Particle-containing fibres |
| CN1064416C (en) * | 1996-05-02 | 2001-04-11 | 上海石油化工股份有限公司 | Method for manufacturing dyeable fine denier polypropylene fibre |
| KR100227221B1 (en) * | 1997-04-01 | 1999-11-01 | 이정국 | A polypropylene resin fiber composition having improved water-resistance and the textile using their fibers |
| 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 |
| 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 |
| EP1115783A1 (en) * | 1998-08-26 | 2001-07-18 | Union Carbide Chemicals & Plastics Technology Corporation | Novel polypropylene compositions |
| US6214915B1 (en) * | 1998-12-10 | 2001-04-10 | General Electric Company | Stabilized thermoplastic compositions |
| NL1014465C2 (en) * | 1999-03-01 | 2002-01-29 | Ciba Sc Holding Ag | Stabilizer combination for the rotomolding process. |
| US6444733B1 (en) * | 1999-03-01 | 2002-09-03 | Ciba Specialty Chemicals Corporation | Stabilizer combination for the rotomolding process |
| JP2002097322A (en) * | 2000-09-25 | 2002-04-02 | Grand Polymer Co Ltd | Polypropylene-based resin composition and molded product therefrom |
| JP4785135B2 (en) * | 2006-07-31 | 2011-10-05 | 三菱レイヨン株式会社 | Polypropylene flame retardant fiber |
| CN101195944B (en) * | 2007-12-11 | 2011-09-07 | 卢宗广 | Non-zillerite environment protection energy-saving diaphragm cloth and weaving method thereof |
| KR101062997B1 (en) | 2009-05-29 | 2011-09-07 | 코오롱글로텍주식회사 | Polypropylene short fibers with high heat resistance and light resistance, manufacturing method thereof, nonwoven fabric made therefrom |
| DE102010006364B4 (en) * | 2010-01-29 | 2015-07-23 | Carl Freudenberg Kg | Use of sterically hindered amines for oxidation-stabilized polyolefins |
| CN106319665A (en) * | 2015-06-15 | 2017-01-11 | 东丽纤维研究所（中国）有限公司 | Colored polypropylene fiber and preparation method thereof |
| EA201991032A1 (en) * | 2016-11-09 | 2019-10-31 | POLYPROPYLENE COMPOSITION | |
| GB2584305B (en) * | 2019-05-30 | 2022-07-13 | Si Group Switzerland Chaa Gmbh | Antidegradant blend |
| CN110229421B (en) * | 2019-07-02 | 2021-11-09 | 中广核俊尔(浙江)新材料有限公司 | High-temperature-resistant injection molding polypropylene material and preparation method and application thereof |
| CN111057288A (en) * | 2019-12-12 | 2020-04-24 | 宿迁联盛科技股份有限公司 | Composition for preventing polyolefin copolymer from photo-aging and polyolefin red-change |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4590231A (en) * | 1983-10-11 | 1986-05-20 | Ciba-Geigy Corporation | Polyolefin compositions stabilized against degradation using hydroxylamine derivatives |
| JPS60190443A (en) * | 1984-03-13 | 1985-09-27 | Mitsui Toatsu Chem Inc | Polypropylene resin composition stable to radiation |
| JP2553537B2 (en) * | 1987-01-23 | 1996-11-13 | 東燃化学 株式会社 | Polypropylene fiber yarn-proofing composition |
| US4876300A (en) * | 1987-12-30 | 1989-10-24 | Ciba-Geigy Corporation | Polyolefin compositions stabilized with long chain N,N-dialkylhydroxylamines |
-
1994
- 1994-03-26 TW TW083102663A patent/TW268052B/zh not_active IP Right Cessation
- 1994-04-06 AT AT0903394A patent/AT405412B/en not_active IP Right Cessation
- 1994-04-06 GB GB9520527A patent/GB2292944B/en not_active Expired - Lifetime
- 1994-04-06 RU RU95120604A patent/RU2126065C1/en active
- 1994-04-06 DE DE4492361A patent/DE4492361C2/en not_active Expired - Lifetime
- 1994-04-06 CA CA002160574A patent/CA2160574C/en not_active Expired - Lifetime
- 1994-04-06 BR BR9406876A patent/BR9406876A/en not_active IP Right Cessation
- 1994-04-06 AU AU62632/94A patent/AU6263294A/en not_active Abandoned
- 1994-04-06 CN CN94191786A patent/CN1051340C/en not_active Expired - Lifetime
- 1994-04-06 NL NL9420023A patent/NL9420023A/en active Search and Examination
- 1994-04-06 JP JP52295194A patent/JP3424080B2/en not_active Expired - Lifetime
- 1994-04-06 DE DE4492361T patent/DE4492361T1/en active Granted
- 1994-04-06 WO PCT/IB1994/000056 patent/WO1994024344A1/en active Application Filing
- 1994-04-06 SK SK1272-95A patent/SK284817B6/en not_active IP Right Cessation
- 1994-04-06 KR KR1019950704499A patent/KR100282620B1/en not_active IP Right Cessation
- 1994-04-14 FR FR9404431A patent/FR2704009B1/en not_active Expired - Lifetime
- 1994-04-14 BE BE9400382A patent/BE1006850A3/en not_active IP Right Cessation
- 1994-04-14 IT ITMI940706A patent/IT1269313B/en active IP Right Grant
-
1995
- 1995-10-03 NO NO953932A patent/NO309683B1/en not_active IP Right Cessation
- 1995-10-04 DK DK199501109A patent/DK175151B1/en not_active IP Right Cessation
-
1998
- 1998-05-28 HK HK98104631A patent/HK1005489A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| IT1269313B (en) | 1997-03-26 |
| ITMI940706A1 (en) | 1995-10-14 |
| GB2292944A (en) | 1996-03-13 |
| DK110995A (en) | 1995-10-04 |
| NO953932D0 (en) | 1995-10-03 |
| SK284817B6 (en) | 2005-12-01 |
| ATA903394A (en) | 1998-12-15 |
| DK175151B1 (en) | 2004-06-21 |
| KR100282620B1 (en) | 2001-02-15 |
| DE4492361T1 (en) | 1997-08-21 |
| CN1051340C (en) | 2000-04-12 |
| CA2160574A1 (en) | 1994-10-27 |
| FR2704009A1 (en) | 1994-10-21 |
| HK1005489A1 (en) | 1999-01-08 |
| KR960702018A (en) | 1996-03-28 |
| TW268052B (en) | 1996-01-11 |
| BR9406876A (en) | 1996-04-02 |
| SK127295A3 (en) | 1996-11-06 |
| BE1006850A3 (en) | 1995-01-03 |
| DE4492361C2 (en) | 2003-10-16 |
| GB2292944B (en) | 1997-12-10 |
| NL9420023A (en) | 1996-01-02 |
| AT405412B (en) | 1999-08-25 |
| RU2126065C1 (en) | 1999-02-10 |
| WO1994024344A1 (en) | 1994-10-27 |
| JP3424080B2 (en) | 2003-07-07 |
| JPH08509031A (en) | 1996-09-24 |
| CN1121362A (en) | 1996-04-24 |
| ITMI940706A0 (en) | 1994-04-14 |
| NO953932L (en) | 1995-10-03 |
| GB9520527D0 (en) | 1995-12-13 |
| FR2704009B1 (en) | 1995-06-30 |
| AU6263294A (en) | 1994-11-08 |
| NO309683B1 (en) | 2001-03-12 |
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