Compositions containing antimicorbial agents in combination with stabilizers

Description

TECHNICAL FIELD
The present invention relates to thermoplastic articles and compositions containing antimicrobial agents and to novel stabilizers for antimicrobial agents.
BACKGROUND ART
It is well known that antimicrobial agents can be incorporated into thermoplastic materials during fabrication so the resulting thermoplastic articles will resist microbial growth. Thermoplastic compounds which are candidates for treatment include materials such as polyamides (nylon 6 or 6,6), polyvinyl chloride (with or without plasticizing agents), polyolefins, polyurethanes, polyethylene terephthalate (polyester), styrene-butadiene rubbers, other elastomers, etc. Antimicrobial agents which are candidates for incorporation into such thermoplastic materials include, but are not limited to, phenoxarsines (including bisphenoxarsines), phenarsazines (including bisphenarsazines), maleimides, isoindole dicarboximides having a sulfur atom bonded to the nitrogen atom of the dicarboximide group, halogenated aryl alkanols, isothiazolinone compounds, and organotin compounds. Others have also been used.
The known microbiocidal phenoxarsine and phenarsazine compounds include compounds represented by the formulas: ##STR1## where X is halogen or thiocyanate, Y is oxygen or sulfur, Z is oxygen or NH, R.sub.1 is halogen, lower alkyl (having from 1 to about 6 carbon atoms), or thiocyanate, and n is from 1 to 4 inclusive. Examples of these phenoxarsines and phenarsazines include, but are not limited to:
10-chlorophenoxarsine;
10-iodophenoxarsine;
10-bromophenoxarsine;
4-methyl-10-chlorophenoxarsine;
2-tert-butyl-10-chlorophenoxarsine;
1,4-dimethyl-10-chlorophenoxarsine
2-methyl-8,10-dichlorophenoxarsine;
1,3,10-trichlorophenoxarsine;
2,6,10-trichlorophenoxarsine;
2,8,10-trichlorophenoxarsine;
1,2,4,10-tetrachlorophenoxarsine;
1,2,4,10-thiocyanatophenoxarsine;
10-thiocyanatophenoxarsine;
10,10'-thiobisphenoxarsine;
10,10'-oxybisphenarsazine;
10,10'-thiobisphenarsazine; and
10,10'-oxybisphenoxarsine (OBPA).
Many of these materials are described in U.S. Pat. No. 3,288,674, issued to Yeager Nov. 19, 1966.
The microbiocidal maleimide compounds are exemplified by N-(2-methylnaphthyl)maleimide.
The microbiocidal isoindole dicarboximides having a sulfur atom bonded to the nitrogen atom of the dicarboximide group contain at least one group having the structure: ##STR2## wherein the hexagonal ring can have one to three sites of ring saturation.
Particular isoindole dicarboximides are the following: ##STR3##
An example of a isothiazolinone compound which has been found useful is 2-(n-octyl-4-isothiazolin-3-one).
Other known antimicrobial agents are: bis(tri-n-butyl tin)oxide (TBTO); pentachlorophenol and its salts; zinc Omadine (a zinc derivative of pyridinethione sold by Olin Chemicals, Stamford, Conn.); 2'-hydroxy-2,4,4'-trichlorodiphenylether (Irgasan DP-300, sold by Ciba-Geigy Corporation, Plastics and Additives Division, Hawthorne, N.Y.); 2,4,5,6-tetrachloroisophthalonitrile (Daconil 2787, sold by Diamond Alkali Company, Cleveland, Ohio); and 2-(4-thiazolyl)benzimidazole (trade name Tektamer 100, sold by the Calgon Division of Merck & Co., Inc., Rahway, N.J.).
In all of these combinations of an antimicrobial agent and a thermoplastic material, the antimicrobial agent must: (1) have sufficient heat stability to avoid being destroyed or losing potency during fabrication; (2) not react with the thermoplastic resin nor any of its additives at elevated processing temperatures and other conditions; and (3) not become volatilized. In addition, the antimicrobial control agent should not impart undesirable features (odor, embrittlement) to the resin at use concentrations. A final requirement is that the composition effectively control microbial growth throughout the intended life of the finished article.
Synthetic fiber manufacture subjects the fiber composition to extremely rigorous conditions. For example, the fiber composition is melted and held at an elevated temperature prior to spinning. When spun, the composition is subjected to extremely high pressures and is further heated by the friction of extrusion. The extruded filaments are then cooled by ventilating them with air. The filaments have a large surface to volume ratio, and thus the composition is extensively exposed to atmospheric oxygen while cooling.
U.S. Pat. No. 3,345,341 claims thermoplastic compositions formed by blending an antimicrobial agent at a suitable ratio with chips of the polymer form prior to fabrication. The compositions are then spun into fibers. The degradation problem and possible solutions are not discussed.
U.S. Pat. No. 2,919,200 (Dubic, et al.) teaches incorporating a bacteriostatic agent in a thermoplastic composition, but simply specifies that the bacteriostatic agent should have a decomposition temperature above the molding temperature of the plastic. Many existing antimicrobial agents do not meet this criterion.
Similarly, U.S. Pat. No. 3,959,556 (Morrison) describes the preparation of synthetic fibers which incorporate an antimicrobial agent, and claims antimicrobial properties are possessed by blends of the treated synthetic fiber with naturally occurring fibers.
U.S. Pat. No. 3,279,986 (Hyman) describes preparation of a thermoplastic sheet material incorporating an antimicrobial agent. The specific antimicrobial agents clamed also are claimed to improve the thermal susceptibility of the sheet material. ("Thermal susceptibility" refers to the well known off-color that results from heating polyvinyl chloride resin materials.)
A weakness of all these patents is their failure to disclose that the antimicrobial agent present in the finished material often lacks some or all of its potency as a result of degradation during processing.
For example, if 500 parts per million (ppm) of OBPA is blended into a nylon composition, which is formed into fiber using conventional melt-spinning technology, only about 100 ppm of active OBPA will be present in the fiber.
This degradation has two important disadvantages. First, much of the antimicrobial agent is wasted so more of the agent must be incorporated in the chosen composition to provide a desired level of performance. Second, the decomposition products of the antimicrobial agent may be more easily released from a thermoplastic composition than the active agent. For example, when nylon fibers containing OBPA are vat dyed, much of the decomposition product (phenoxyarsenic acid) formed as a result of fiber fabrication migrates into the dye bath, necessitating removal before the dye effluent is released into the environment. If the amount of decomposition of OBPA during fiber formulation were reduced, the leaching of the phenoxyarsenic acid from fibers would be reduced.
Further, some known biological agents are not selected in these patents because the omitted agents are known to be insufficiently resistant to thermal inactivation.
The literature discloses using antioxidants in polymeric plastic compositions. There is a wide spectrum of needs for such antioxidants in different polymers and plastic compounds. For example, some resin compositions cannot be fabricated at all without antioxidants, while polyvinyl chloride compositions and polyamide (such as nylon) compositions do not benefit substantially from inclusion of an antioxidant except during high-temperature fabrication.
The following materials are known to act as antioxidants for plastic compositions:
______________________________________MONOPHENOLS______________________________________1. 2,6-Di-t-butyl-p-cresol or2,6-Di-t-butyl-4-methylphenol ##STR4## Mole Weight 220 White powder, flakes, granules or pellets Melt Point 69-70.degree. C. Specific Gravity 1.04-1.05______________________________________TRADENAME SUPPLIER______________________________________BHT KoppersCAO-1 Sherwin-WilliamsCAO-3 Sherwin-WilliamsDBPC KoppersDBPC-80 (1) KoppersIonol ShellIonol CP ShellLowinox BHT LowiNaugard BHT UniroyalPermanax BHT VulnaxSustane BHT UOPSustane 1-F UOPVanox PC VanderbiltVanox PC-X VanderbiltVulkanox KB Mobay______________________________________ (1) 80%
2. Styrenated phenol ##STR5## Viscous straw colored liquid Specific Gravity 1.08General purpose non-staining antioxidantused in rubber and latex.______________________________________TRADENAME SUPPLIER______________________________________WINGSTAY S GOODYEARWINGSTAY S Powder (1) GOODYEARAntioxidant SP (2) HarwickLowinox P24S LowiNaugard SP UniroyalNaugard SP Powder (3) UniroyalNevastain 21 NevilleNevastain 2170 (3) NevillePermanax SP (4) VulnaxPermanax SP(L) VulnaxStabilite SP 49-464 (5) ReichholdStyrenated Phenol Ferro/ProductolVanox 102 VanderbiltVanox 1002 Vanderbilt______________________________________ (1) 65% Active on inert carrier (2) Active concentration not listed Specific Gravity 1.56 (3) 70% Active on inert carrier Specific Gravity 1.32 (4) 60% Active on inert carrier (5) Listed as `polymeric styrenated
3. 2- and 3-t-Butyl-4-hydroxyanisole or2- and 3-t-Butyl-4-methoxyphenol ##STR6## Mole Weight 180 White or off-white tablets or pellets Melt Point 48-57.degree. C. Specific Gravity 1.04General purpose antioxidantfrequently used in foods.______________________________________TRADENAME SUPPLIER______________________________________Sustane BHA UOPTenox BHA Eastman______________________________________4. Alkylated hindered phenols ##STR7## Viscous liquids varying in color from pale straw to brownR's may be methyl or other alkyl groups, the larger ones usuallybeing tertiary. Frequently more than one type of group is present.General purpose antioxidants and polymer stabilizers for rubberand plastics. These generally have good color and stain______________________________________properties. SPECIFICTRADENAME SUPPLIER GRAVITY______________________________________WINGSTAY C GOODYEAR 1.01WINGSTAY T GOODYEAR 0.91WINGSTAY V GOODYEAR 1.02Antioxidant 431 Uniroyal 1.08CAO-42 Sherwin-Williams 0.93Cyanox LF Cyanamid 1.06Cyanox 251 (1) Cyanamid 1.39Cyanox 1735 Cyanamid 0.90Ethyl Antioxidant 733 Ethyl 0.94Ethyl Antioxidant 735 Ethyl 0.95Hydrochem AO-535C Continental 0.90 ProductsLowinox P24A LowiNaugard 431 Uniroyal 1.08Permanax WSL Vulnax 1.00Permanax WSL Powder Vulnax 1.26Prodox 246 Ferro/Productol 0.931Prodox 340 Ferro/Productol 0.958Prodox 345 Ferro/Productol 0.959Stabilite White Powder 49-454 Reichhold 1.32Stabilite White Liquid 49-455 Reichhold 0.91Stabilite 49-470 (2) ReichholdStabiwhite Powder CP Hall 1.32Uvinox 1494 GAF 0.90Vanox 100 Vanderbilt 1.03Vanox 100 Powder Vanderbilt 1.37Vulkanox DS/F (3) Mobay 1.3______________________________________ (1) Cream white powder contains an inert carrier (2) White powder (3) Contains 50% inorganic filler
5. 4-(Hydroxymethyl)-2,6-di-t-butylphenol ##STR8## Mole Weight 236.4 Off-white crystalline powder Melt Point 138.degree. C.______________________________________TRADENAME SUPPLIER______________________________________Ethyl Antioxidant 754 Ethyl______________________________________6. `Fortified` hindered phenol(Structured not disclosed) White powder Melt Point 95.degree. C. min. Specific Gravity 1.30General purpose phenolic antioxidant used in compoundingwhere color and staining are critical.______________________________________TRADENAME SUPPLIER______________________________________Vanox ZS Vanderbilt______________________________________7. 2,6-Di-t-butyl-4-sec-butylphenol ##STR9## Mole Weight 262 Amber liquid Specific Gravity______________________________________ 0.90TRADENAME SUPPLIER______________________________________Isonox 132 SchenectadyVanox 1320 Vanderbilt______________________________________
__________________________________________________________________________BISPHENOLS AND THIOBISPHENOLS__________________________________________________________________________1. 2,2'-Methylenebis(6-t-butyl-p-cresol) or2,2'-Methylenebis(4-methyl-6-t-butylphenol) ##STR10## Mole Weight 341 White or light colored powder Melt Point 133.degree. C. Specific Gravity 1.04-1.08Antioxidant for rubber compounding. Some use in latex and plastics.Essentially non-staining, but can cause slight pink discoloration.TRADE NAME SUPPLIER__________________________________________________________________________Antioxidant MBP-5 AcetoCAO-5 Sherwin-WilliamsCAO-14 Sherwin-WilliamsCyanox 2246 CyanamidLowinox 22M46 LowiOxy-Chek 114 FerroSantowhite PC MonsantoVanox 2246 VanderbiltVulkanox BKF Mobay__________________________________________________________________________2. 2,2'-Methylenebis(4-ethyl-6-t-butylphenol) ##STR11## Mole Weight 369 White to cream powder Melt Point 119-125.degree. C. Specific Gravity 1.10General purpose antioxidant weaker than (B-1), but less discoloring.TRADE NAME SUPPLIER__________________________________________________________________________Cyanox 425 Cyanamid__________________________________________________________________________3. 4,4'-Methylenebis(2,6-di-t-butylphenol) ##STR12## Mole Weight 424 Light yellow crystalline powder elt Point 154-155.degree. C. Specific Gravity 1.01General purpose antioxidant-stabilizer. Also used in resins.TRADE NAME SUPPLIER__________________________________________________________________________Antioxidant MO14 AcetoEthyl Antioxidant 702 EthylEthyl Antioxidant 728 (1) EthylLowinox 002 LowiProdox B-113 Ferro/Productol__________________________________________________________________________ (1) `Soluble form`-
4. Miscellaneous bisphenols - structures not revealed SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER__________________________________________________________________________Cyanox 53 (1) White powder 1.74 CyanamidNaugawhite Amber liquid 0.96 UniroyalNaugawhite Powder (1) Tan powder 1.19 UniroyalPermanax WSO White powder 1.00 VulnaxWytox PAP Amber liquid 0.92 OlinWytox PSP-S (1) Tan powder OlinWytox PAP-SE (2) Amber liquid 0.92 Olin__________________________________________________________________________ (1) `On an inert carrier`- (2) Self emulsifiable form
5. 2,2'-Ethylidenebis(4,6-di-t-butylphenol) ##STR13## Mole Weight 438 White powder Melt Point 161-164.degree. C. Specific Gravity 1.01Antioxidant for rubber and plastics compounding.TRADE NAME SUPPLIER__________________________________________________________________________Isonox 129 SchenectadyVanox 1290 Vanderbilt__________________________________________________________________________6. 2,2'-Methylenebis(4-methyl-6-(1-methylcyclohexyl)phenol) ##STR14## Mole Weight 422 Off-white powder Melt Point 120-130.degree. C. Specific Gravity 1.17Antioxidant for rubber and plastics compounding.TRADE NAME SUPPLIER__________________________________________________________________________Nonox WSP ICIPermanax WSP VulnaxPermanax WSP (PQ) Vulnax__________________________________________________________________________7. 4,4'-Butylidinebis(6-t-butyl-m-cresol) or4,4'-Butylidenebis(6-t-butyl-3-methylphenol) ##STR15## Mole Weight 382.5 White powder Melt Point 209.degree. C. Specific Gravity 1.03Antioxidant for rubber, latex and plastics compounding.TRADE NAME SUPPLIER__________________________________________________________________________Lowinox 44B25 LowiSantowhite Powder Monsanto__________________________________________________________________________8. Polybutylated Bisphenol A Amber liquid Specific Gravity 0.945-0.965Antioxidant for rubber compounding and raw polymer stabilization.TRADE NAME SUPPLIER__________________________________________________________________________Agerite Superlite VanderbiltAgerite Superlite Solid (1) VanderbiltLowinox P22B LowiVanox 1003 VanderbiltVanox 1004 (Powder) (1) Vanderbilt__________________________________________________________________________ (1) 75% Agerite Superlite or Vanox 1003 and 25% inert carrier Specific Gravity 1.26
9. 4,4'-Thiobis(6-t-butyl-m-cresol) or4,4'-Thiobis(6-t-butyl-3-metyhylphenol) ##STR16## Mole Weight 358.5 Light colored powder Melt Point 150.degree. C. Specific Gravity 1.06-1.12Antioxidant for rubber, latex and plastics compounding. Widely used inCR.Activates CR cure systems.TRADE NAME SUPPLIER__________________________________________________________________________Antioxidant TBM6 (1) AcetoLowinox 44S36 LowiSantonox (2) MonsantoSantowhite Crystals MonsantoSantowhite MK (3) Monsanto__________________________________________________________________________ (1) Technical and pure grades (2) More pure form of Santowhite (3) Reaction product grade
10. 4,4'-Methylenebis(2,6-dimethylphenol) ##STR17## Mole Weight 256TRADE NAME SUPPLIER__________________________________________________________________________Lowinox 44M26 Lowi__________________________________________________________________________11. 1,1'-Thiobis(2-naphthol) ##STR18## Mole Weight 318 Light yellow powder Melt Point 218.degree. C. Min.TRADE NAME SUPPLIER__________________________________________________________________________SAO-30 Southland__________________________________________________________________________12. Methylene bridged polyalkylphenol Solid Specific Gravity 1.02TRADE NAME SUPPLIER__________________________________________________________________________Ethyl Antioxidant 738 Ethyl__________________________________________________________________________13. 2,2'-Thiobis(4-methyl-6-t-butylphenol) ##STR19## Mole Weight 359TRADE NAME PHYS FORM MELT POINT SUPPLIER__________________________________________________________________________SAO-4 Light yellow powder 70.degree. C. Min. SouthlandSAO-6 White powder 83-86.degree. C. Southland__________________________________________________________________________14. Sulfur containing hindered phenol cyanurate White powder Melt Point 190-194.degree. C.TRADE NAME SUPPLIER__________________________________________________________________________SAO-44 Southland__________________________________________________________________________15. 2.2'-Isobutylidenebis(4,6-dimethylphenol) ##STR20## Mole Weight 298 White powder Specific Gravity 1.12TRADE NAME SUPPLIER__________________________________________________________________________Lowinox 22IB46 LowiVulkanox NKF Mobay__________________________________________________________________________16. 2,2'-Methylenebis(4-methyl-6-cyclohexylphenol) ##STR21## Mole Weight 393 Melt Point 125.degree. C. Min. Specific Gravity 1.08TRADE NAME SUPPLIER__________________________________________________________________________Vulkanox ZKF Mobay__________________________________________________________________________
______________________________________POLYPHENOLS______________________________________1. Butylated reaction product of p-cresol and dicyclopentadiene ##STR22## Average Mole Weight 600-700 White powder or amber flake Melt Point 100.degree. C. Specific Gravity 1.10Non-staining antioxidant for general and high temperatureapplications. Especially recommended for NR, IR, SBR,CR and carboxylated polymers. Widely used in latex.TRADE NAME SUPPLIER______________________________________WINGSTAY L Flake GOODYEARWINGSTAY L Powder GOODYEAR______________________________________2. Tetrakis(methylene 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) methane or Tetrakis(methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane ##STR23## Mole Weight 1178 White crystalline powder Melt Point 110-125.degree. C. Specific Gravity 1.45TRADE NAME SUPPLIER______________________________________Irganox 1010 CIBA-GEIGY______________________________________3. 1,3,5-Trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene ##STR24## Mole Weight 775 White crystalline powder Melt Point 244.degree. C.High performance antioxidant for plastics, rubber, resinsand waxes.TRADE NAME SUPPLIER______________________________________Ethyl Antioxidant 330 Ethyl______________________________________4. 1,3,5-Tris(3,5-di-t-butyl-4-hydroxybenzyl)-s-triazine-2,4,6(1H,3H,5H)trione or 1,3,5-Tris(3,5-di-t-butyl-4-hydroxy-benzyl) isocyanurate ##STR25## White crystalline powder Melt Point 217-225.degree. C. Specific Gravity 1.03High temperature antioxidant recommended for plastics.TRADE NAME SUPPLIER______________________________________Agerite GT VanderbiltGood-rite 3114 GoodrichVanox GT Vanderbilt______________________________________5. 3:1 Condensate of 3-methyl-6-t-butylphenol with crotonaldehyde White crystalline powder Melt Point 182.5-188.degree. C.High performance antioxidant - recommended for plastics.TRADE NAME SUPPLIER______________________________________Topanol CA ICI______________________________________6. Phenolic condensation products with structures not revealed.General purpose antioxidants for rubber and plasticscompounding. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Akrochem White powder 1.04 AkronAntiox 33 (M P 100.degree. C. Chemical Min.)Akrochem White powder 1.05 AkronAntiox 36 (M P 148.degree. C.) ChemicalAkrochem White powder 1.04 AkronAntiox 51 (M P 118.degree. C.) ChemicalLowinox 22CP46 Powder LowiMark 328 White powder ArgusNevastain A Liquid 1.08-1.09 NevilleNevastain B Flake 1.09-1.11 Neville (M P 55.degree. C.)Nevastain 76 Amber flake 1.1 Neville (M P 134.degree. C.)Stabilite 49-466 Powder (M P 1.04 Reichhold 110--110.degree. C.)Stabilite 49-467 Powder 1.05 Reichhold (M P 148.degree. C.)Wytox PDA-S Tan powder - Olin contains inert carrierWytox PMW Amber powder 1.05-1.07 Olin (M P 122.degree. C.)______________________________________7. 4-((4,6-Bis(octylthio)-2-triazin-2-yl)amino)-2,6-di-t-butylphenol or2,4-(Bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)1,3,5-triazine ##STR26## White powder Melt Point 93-98.degree. C.TRADE NAME SUPPLIER______________________________________Irganox 565 CIBA-GEIGY______________________________________Phenol/aldehyde condensatesGeneral purpose antioxidants. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Permanax EXP Brown solid 1.07 Vulnax (M P 60.degree. C.)Permanax WMP (1) Cream powder 1.54 Vulnax______________________________________ (1) Contains an inert carrier
______________________________________HYDROQUINONE DERIVATIVES______________________________________1. 2,5-Di-t-amylhydroquinone ##STR27## Mole Weight 250 Off-white crystalline powder Melt Point 179.degree. C. Specific Gravity 1.02-1.05Polymer stabilizer and shortshop; also used in adhesives;slightly discoloring.TRADE NAME SUPPLIER______________________________________Santovar A Monsanto______________________________________2. t-Butylhydroquinone ##STR28## Mole Weight 166 Off-white crystalline powder Melt Point 127-129.degree. C.Polymer stabilizer and shortshop.TRADE NAME SUPPLIER______________________________________Tenox TBHQ Eastman______________________________________3. Alkylated hydroquinone (structure not specified) Viscous liquid (partially crystallizes) Specific Gravity 0.90 @ 38.degree. C.Antioxidant stabilizer for synthetic rubbers and plastics.TRADE NAME SUPPLIER______________________________________Antioxidant 451 Uniroyal______________________________________
______________________________________PHOSPHITES AND PHOSPHITE BLENDS______________________________________1. Tris(nonylphenyl) phosphite ##STR29## Amber, viscous liquid Specific Gravity 0.98Non-staining stabilizer for raw polymer SBR and plastics.TRADE NAME SUPPLIER______________________________________Interstab CH-55 InterstabLowinox TNPP LowiMark 1178 ArgusMark 1178B (1) ArgusNaugard P UniroyalNaugard PHR (1) UniroyalPolygard UniroyalPolygard HR (1) UniroyalWeston TNPP Borg-WarnerWeston 399 (2) Borg-WarnerWeston 399B (2) Borg-WarnerWytox 312 OlinWytox 320 Olin______________________________________ (1) Hydrolysis resistant grades (2) More hydrolytically stable, containing TIPA
2. Bis(2,4-di-t-butyl)pentaerythritol diphosphite ##STR30## Mole Weight 604 White crystalline solid Melt Point 160-175.degree. C.Antioxidant-stabilizer for rubbers and plastics.TRADE NAME SUPPLIER______________________________________Weston MDW-626 Borg-Warner______________________________________3. Distearyl pentaerythritol diphosphite ##STR31## Mole Weight 732 White flake Melt Point 40.degree. C. Specific Gravity 0.94-0.96Antioxidant for plastics.TRADE NAME SUPPLIER______________________________________Weston 618 Borg-WarnerWeston 619 (1) Borg-Warner______________________________________ (1) More hydrolytically stable grade, containing TIPA
4. `Polymeric` phosphites-structures not disclosedGeneral purpose antioxidants andstabilizers for rubber and plastics. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Wytox 345 Yellow liquid 0.99 OlinWytox 345-S (1) White powder OlinWytox 438 Yellow liquid 1.01 OlinWytox 438-S (1) Gray powder OlinWytox 540 Liquid 1.003 OlinWytox 540-S (1) Gray powder Olin______________________________________ (1) Solid form on a carrier
5. Phosphited phenols and bisphenols-structures not revealedGeneral purpose antioxidants for rubber and plastics. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Agerite Geltrol Liquid 0.955-0.975 VanderbiltNaugard 492 Liquid 1.008 UniroyalVanox 13 Liquid 0.93 VanderbiltVanox 1005 Liquid 0.955-0.975 VanderbiltVanox 1013 Liquid 0.93 VanderbiltWytox 604 Liquid 0.89-0.93 OlinWytox 604-LMS Liquid 0.948 OlinWytox 604-S (1) Gray powder Olin______________________________________ (1) Solid form
______________________________________THIOESTERS______________________________________6. Phosphite/phenolic antioxidant blendsTRADE NAME SUPPLIER______________________________________Irganox B215 (1) CIBA-GEIGYIrganox B225 (2) CIBA-GEIGYIrganox B900 (3) CIBA-GEIGYIrganox B1171 (4) CIBA-GEIGYWeston 800 (5) Borg-WarnerWeston 801 (6) Borg-WarnerWeston 802 (7) Borg-Warner______________________________________ Blends of tris(2,4-di-t-butylphenyl) phosphite and a phenolic antioxidant as follows: (1) 2:1 Blend with tetrakis(methylene(3,5di-t-butyl-4-hydroxy hydrocinnamate))methane(C2) (2) 1:1 Blend with tetrakis(methylene(3,5di-t-butyl-4-hydroxy hydrocinnamate))methane(C2) (3) 4:1 Blend with octadecyl(3,5di-t-butyl-4-hydroxybenzyl)phosphonate(G-1) (4) 1:1 Blend with 1,6hexamethylenebis-(3,5-di-t-butyl-4-hydroxy hydrocinnamide)(G5) Blends of distearyl pentaerythritol diphosphite(E3) and tetrakis(methylen 3(3,5-di-t-butyl-4-hydroxyphenyl)propionate)methane as follows: (5) 1:1 Blend (6) 2:1 Blend (7) 3:1 Blend
1. Dilauryl thiodipropionate or Didodecyl 3,3'-thiodipropionate ##STR32## Mole Weight 515 White waxy solid Melt Point 40-45.degree. C. Specific Gravity 1.01Antioxidant for polyolefins and other plastics.TRADE NAME SUPPLIER______________________________________Argus DLTDP ArgusCarstab DLTDP CarstabCyanox LTDP CyanamidEvanstab 12 EvansLowinox DLTDP LowiNonox DLTDP ICI______________________________________2. Distearyl thiodipropionate or Dioctadecyl 3,3'-thiodipropionate ##STR33## Mole Weight 682 White waxy solid Melt Point 57-67.degree. C. Specific Gravity 0.985Antioxidant for polyolefins and other plastics.TRADE NAME SUPPLIER______________________________________Argus DSTDP ArgusCarstab DSTDP CarstabCyanox STDP CyanamidEvanstab 18 EvansNonox DSTDP ICI______________________________________3. Dimyristyl thiodipropionate ##STR34## Mole Weight 571 White waxy solid Melt Point 44-48.degree. C.Antioxidant for polyolefins and other plastics.TRADE NAME SUPPLIER______________________________________Argus DMTDP ArgusCarstab DMTDP CarstabCYanox MTDP CyanamidEvanstab 14 Evans______________________________________4. Ditridecyl thiodipropionate ##STR35## Mole Weight 543 Colorless liquid Specific Gravity 0.936TRADE NAME SUPPLIER______________________________________Argus DTDTDP ArgusCyanox 711 CyanamidEvanstab 13 Evans______________________________________5. Mixed esters(lauryl and stearyl) of thiodipropionic acid ##STR36## Mole Weight 599 White crystalline powder or flakes Melt Point 50.degree. C.TRADE NAME SUPPLIER______________________________________Cyanox 1212 Cyanamid______________________________________6. Pentaerythritol tetrakis(3-(dodecylthio)propionate) ##STR37## Mole Weight 1162 White solid Melt Point 50.degree. C. Min.Antioxidant for polyolefins and other plastics.TRADE NAME SUPPLIER______________________________________Seenox 412-S Argus______________________________________7. Blend of a phenolic and thioester type antioxidant. White powder Specific Gravity 1.04, 1.76 (1)Antioxidant systems for polyolefins.TRADE NAME SUPPLIER______________________________________Vanox 1030 VanderbiltVanox 1040 (1) Vanderbilt______________________________________ (1) Contains a mineral deactivator for mineral filled compounds.
__________________________________________________________________________MULTIFUNCTIONAL NON-STAINING ANTIOXIDANTS__________________________________________________________________________1. O,ODi-n-octadecyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate ##STR38## Mole Weight 805 White crystalline powder Melt Point 45.degree. C. Min. Specific Gravity 0.96Antioxidant, stabilizer for plastics.TRADE NAME SUPPLIER__________________________________________________________________________Irganox 1093 CIBA-GEIGY__________________________________________________________________________2. 1,6-Hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamate)1,6-Hexamethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) ##STR39## Mole Weight 639 Off-white crystalline powder Melt Point 94-108.degree. C.General purpose antioxidant for plastics and elastomers.TRADE NAME SUPPLIER__________________________________________________________________________Irganox 259 CIBA-GEIGY__________________________________________________________________________3. Thiodiethylene bis(3,5-di-t-butyl-4-hydroxy)hydrocinnamate orThiodiethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) ##STR40## Mole Weight 642 White crystalline powder Melt Point 63.degree. C. Min. Specific Gravity 1.19Antioxidant for plastic and elastomers.TRADE NAME SUPPLIER__________________________________________________________________________Irganox 1035 CIBA-GEIGY__________________________________________________________________________4. Octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate orOctadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate ##STR41## Mole Weight 531 White crystalline powder Specific Gravity 1.02 Melt Point 49-54.degree. C.Antioxidants for plastics and elastomers.TRADE NAME SUPPLIER__________________________________________________________________________Irganox 1076 CIBA-GEIGY__________________________________________________________________________5. N,N'Hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide) or N,N'Hexamethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide) ##STR42## Mole Weight 637 White crystalline powder Specific Gravity 1.05 Melt Point 156-162.degree. C.Antioxidants for polyamides, plastics and elastomers.TRADE NAME SUPPLIER__________________________________________________________________________Irganox 1098 CIBA-GEIGY__________________________________________________________________________6. 3,5-Di-t-butyl-4-hydroxyhydrocinnamic acid triester with1,3,5-Tris(2-hydroxyethyl)-s-triazine-2,4,6-(1H,3H,5H)trione ##STR43## ##STR44## Mole Weight 1042 White crystalline powder Specific Gravity 0.921 Melt Point 123-131.degree. C.Antioxidant for plastics.TRADE NAME SUPPLIER__________________________________________________________________________Good-rite 3125 GoodrichAgerite SKT, Vanox SKT Vanderbilt__________________________________________________________________________7. NButyryl-p-aminophenol or N(4-Hydroxyphenyl)butyramide ##STR45## Mole Weight 179 White powder elt Point 136-141.degree. C.Antioxidants for plastics and elastomers.TRADE NAME SUPPLIER__________________________________________________________________________Suconox 4 Hexel__________________________________________________________________________8. NPelargonoyl-p-aminophenol or N(4-Hydroxyphenyl)pelargonamide ##STR46## Mole Weight 249 White powder elt Point 121-125.degree. C.Antioxidant for plastics and elastomers.TRADE NAME SUPPLIER__________________________________________________________________________Suconox 9 Hexel__________________________________________________________________________9. NLauroyl-p-aminophenol or N(4-Hydroxyphenyl)dodecanamide ##STR47## Mole Weight 291 White powder Melt Point 130-134.degree. C.Antioxidant for plastics, butyl rubber and elastomers.TRADE NAME SUPPLIER__________________________________________________________________________Suconox 12 Hexel__________________________________________________________________________10. NStearoyl-p-aminophenol or N(4-Hydroxyphenyl)stearamide ##STR48## Mole Weight 376 White powder elt Point 130-134.degree. C.Antioxidant for polyethylene and polyamides.TRADE NAME SUPPLIER__________________________________________________________________________Suconox 18 Hexel__________________________________________________________________________11. 2,6-Di-t-butyl-alpha-dimethylamino-p-cresol or2,6-Di-t-butyl-4-(dimethylaminomethyl)phenol ##STR49## Mole Weight 263 Light yellow crystalline powder Melt Point 94.degree. C.Antioxidant for plastics and elastomers.TRADE NAME SUPPLIER__________________________________________________________________________Ethyl Antioxidant 703 Ethyl__________________________________________________________________________12. 1,3,5-Tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione ##STR50## ##STR51## Mole Weight 699 Off-white powder Melt Point 145-155.degree. C.TRADE NAME SUPPLIER__________________________________________________________________________Cyanox 1790 Cyanamid__________________________________________________________________________13. Nickel bis(Oethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate) ##STR52## Mole Weight 714 Tan-light green powder Melt Point 180.degree. C. Min.Antioxidant/UV absorber for plastics.TRADE NAME SUPPLIER__________________________________________________________________________Irgastab 2002 CIBA-GEIGY__________________________________________________________________________14. 2,2'-Oxamidobisethyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate ##STR53## Mole Weight 697 Off-white powder Melt Point 173.degree. C.Antioxidant and metal deactivator.TRADE NAME SUPPLIER__________________________________________________________________________Naugard XL-1 Uniroyal__________________________________________________________________________15. Phenolic antioxidant/metal deactivator - undisclosed composition. SPECIFICTRADE NAME GRAVITY MELT POINT SUPPLIER__________________________________________________________________________Irganox MD-1024 1.12 224.degree. C. Min. CIBA-GEIGY__________________________________________________________________________16. Tris(2-t-butyl-4-(2-methyl-4-hydroxy-5-t-butylphenylthio)-5-methyl)phenylphosphite ##STR54## Mole Weight 1103Antioxidant and metal deactivator SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER__________________________________________________________________________Antioxidant VP OSP 1 White powder 1.10 Hoechst__________________________________________________________________________17. Bis(3,3-bis(4-hydroxy-3-t-butylphenyl)butanoic acid)glycolester Mole Weight 795 Melt Point 170.degree. C. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER__________________________________________________________________________Hostanox 03 White powder 1.1 Hoechst__________________________________________________________________________18. Tetrakis(2,4-di-t-butylphenyl)4,4'-biphenylylenediphosphonite ##STR55## Mole Weight 1035 SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER__________________________________________________________________________Sandostab P-EPQ 75.degree. C. 1.045 Sandoz__________________________________________________________________________19. n-Propyl gallate or n-Propyl 3,4,5-tri-hydroxybenzoate ##STR56## Mole Weight 212 White powder Melt Point 146-148.degree. C.TRADE NAME SUPPLIER__________________________________________________________________________Tenox PG Eastman__________________________________________________________________________20. Calcium bis(Oethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate) ##STR57## Mole Weight 647 Off-white powder Melt Point >260.degree. C.Antioxidant/metal deactivatorTRADE NAME SUPPLIER__________________________________________________________________________Irganox 1425 CIBA-GEIGY__________________________________________________________________________21. Phenolic Antioxidant - composition undisclosed.Antioxidant/metal deactivator.TRADE NAME PHYSICAL FORM SUPPLIER__________________________________________________________________________Lowinox 22CP46-MD Off-white powder Lowi__________________________________________________________________________
______________________________________MISCELLANEOUS UNCLASSIFIEDNON-STAINING ANTIOXIDANTS AND BLENDS______________________________________1. 1.2-Mercapto-4(5)-methylbenzimidazole ##STR58## Mole Weight 164 Yellow-white powder Specific Gravity 1.25 Melt Point 270.degree. C.and ##STR59##Antioxidant, synergist and metal deactivator.TRADE NAME SUPPLIER______________________________________Vulkanox MB-2/MG Mobay______________________________________2. Zinc salt of 2-mercaptobenzimidazole ##STR60## White powder Specific Gravity 1.75 Melt Point > 300.degree. C. with decomposition.Antioxidant and synergist.TRADE NAME SUPPLIER______________________________________Akrochem Antioxidant 58 Akron ChemicalNaugard ZMB Uniroyal______________________________________3. 2-Mercapto-4-methylbenzimidazole, zinc salt,2-Mercapto-5-methylbenzimidazole, zinc salt ##STR61## SPECIFICTRADE NAME GRAVITY MELT POINT SUPPLIER______________________________________Vulkanox ZMB-2/C 1.75 >300.degree. C. Mobay______________________________________4. Antioxidants of undisclosed composition, including blends.TRADE NAME PHYS FORM SUPPLIER______________________________________Mark 1220 Yellow liquid ArgusMark 1475 (1) White powder ArgusMark 2112 White powder ArgusMark 2183 (1) Tan powder Argus______________________________________ (1) Antioxidant/chelator. -
5. Phosphite/phenolic antioxidant blends SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Mark 1409 Liquid 0.99 ArgusMark 1409-S (1) Granules 1.18 Argus______________________________________ (1) Solid form of Mark 1409 -
6. Thioester/phenolic antioxidant blendsGeneral purpose antioxidants used mainly in plastics. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Mark 158 Yellow liquid 0.982 ArgusMark 1589 White powder 1.17 ArgusMark 1589B White powder 1.17 Argus______________________________________7. 2-Mercaptotoluimidazole ##STR62## Mole Weight 164 Melt Point 250.degree. C. Min.Non-staining antioxidant and synergist. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Vanox MTI Tan powder 1.33 Vanderbilt______________________________________8. Zinc 2-mercaptotoluimidazole ##STR63## Mole Weight 391Non-staining antioxidant and synergist. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Vanox ZMTI Tan powder 1.69 Vanderbilt Melt Point > 300.degree. C.______________________________________9. Dioctadecyl disulfide H.sub.38 C.sub.18SSC.sub.18 H.sub.38 Mole Weight 571 Melt Point 53-58.degree. C. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Antioxidant SE10 White powder 0.85@55.degree. C. Hoechst______________________________________10. Blends including a phenolic antioxidant-undisclosed composition. SPECIFIC MELTTRADE NAME GRAVITY POINT SUPPLIER______________________________________Antioxidant AO-19 1.03 110-200.degree. C. SovereignAntioxidant 35 1.04 105-115.degree. C. SovereignPowderAntioxidant 872 1.03 122.degree. C. Sovereign______________________________________11. Blend of non-staining antioxidants SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Permanax CNS Cream powder 1.25 Vulnaz Melt Point 298.degree. C.______________________________________12. Metal aromatic sulfonateMineral deactivator. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Vanox 3240 Brown liquid 0.98 VanderbiltVanox 3245 Brown flake 1.12 Vanderbilt______________________________________
______________________________________NAPHTHYLAMINES______________________________________1. NPhenyl-alpha-naphthylamine ##STR64## Mole Weight 219 Tan-purple powder Melt point 50-59.degree. C. Specific Gravity 1.16-1.20TRADE NAME SUPPLIER______________________________________Additin 30 MobayAkrochem Antioxidant PANA Akron ChemicalNaugard PAN Uniroyal______________________________________2. NPhenyl-beta-naphthylamine (Commonly called `PBNA`) ##STR65## Mole Weight 219 Dark Solid Melt Point 105-106.degree. C. Specific Gravity 1.18-1.24Powerful staining antioxidant exstensively used in Europe.No known suppliers in the USA.______________________________________
__________________________________________________________________________DIPHENYLAMINE AND OTHER DIARYLAMINE DERIVATIVES__________________________________________________________________________1. p-Oriented styrenated diphenylamine ##STR66##Mostly di substituted with some mono and tri substituted species.Some ortho substitution.Highly active non-staining, mildly discoloring amine for natural andsyntheticpolymers and compounds. TRADE NAME SUPPLIER__________________________________________________________________________ WINGSTAY 29 GOODYEAR WINGSTAY 29 Powder (1) GOODYEAR Lowinox SDA (2) Lowi Vulkanox DDA (2) Mobay__________________________________________________________________________ (1) Solid form of WINGSTAY 29 70% active Specific Gravity 1.53 (2) Orientation and amount of styrenation not listed.
2. Octylated diphenylamines ##STR67##General purpose semi-staining antioxidants for polymers and compounds SPECIFICTRADE NAME PHYS FORM MELT POINT GRAVITY SUPPLIER__________________________________________________________________________Agerite Gel (1) Tan waxy solid 40-50.degree. C. 0.94 VanderbiltAgerite Stalite S Tan powder 89-103.degree. C. 1.02 VanderbiltAkrochem Antiox S Brown granules 88.degree. C. Min. 1.00 Akron ChemicalCyanox 8 Gray flakes 75-85.degree. C. 0.98 CyanamidFlectol ODP Tan powder 89-103.degree. C. 0.99 MonsantoOctamine Tan solid 85.degree. C. Min. 0.99 UniroyalPennox ODP Tan powder 88-98.degree. C. 1.02 PennwaltPermanax OD Tan granules 90.degree. C. 1.12 VulnaxVanox 12 Tan granules 94-100.degree. C. 1.01 VanderbiltVanox 1081 Tan granules 94-100.degree. C. 1.02 VanderbiltVulkanox OCD Tan granules 90.degree. C. 1.12 Mobay__________________________________________________________________________ (1) Contains 25% wax
3. Other alkylated diphenylamines ##STR68##General purpose semi-staining antioxidants. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER__________________________________________________________________________Agerite NEPA (1) Amber liquid 0.935 VanderbiltAgerite Stalite (2) Dark liquid 1.01 VanderbiltPennox A (2) Dark liquid 0.995-1.025 PennwaltPermanax HD (3) Brown liquid 0.97 VulnaxPermanax HD(SE) (4) Brown liquid 0.97 VulnaxPolylite (5) Dark liquid 0.95 UniroyalVanox 1001 (1) Amber liquid 0.935 VanderbiltWytox ADP-F (1) Gray flake 0.99 Olin__________________________________________________________________________ (1) Alkylation not specified (2) Octylated (3) Heptylated (4) Self emulsifying form (5) Nonylated
4. High temperature reaction products of diphenylamine and acetonePowerful amine antioxidants for rubber compounds used frequently toimpart high temperature resistance. Rather severe staining SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER__________________________________________________________________________Agerite Superflex (1) Dark liquid 1.10 VanderbiltAgerite Superflex Dk br powder 1.33 VanderbiltSolid G (3)Agerite Superflex Dk brown rods 1.34 VanderbiltSolid Rodform (2)BLE-25 Dark br liquid 1.10 UniroyalBLE-75 Dk br powder 1.33 UniroyalPermanax BL Brown liquid 1.09-1.10 VulnaxPermanax BLN Brown liquid 1.09-1.10 VulnaxPermanax BLW (5) Brown solid 1.26 Vulnax__________________________________________________________________________ (1) Contains 20% diphenylamine (2) 32.5% Inert carrier (3) 15% Diphenylamine, 25% inert carrier (4) 75% Active on microcel (5) Contains a silicate carrier
5. Low temperature reaction product of diphenylamine and acetone Brown-green powder Specific Gravity 1.15General purpose antioxidant.TRADE NAME MELT POINT SUPPLIER__________________________________________________________________________Aminox 85-95.degree. C. UniroyalPermanax B 75-90.degree. C. Vulnax__________________________________________________________________________6. Diarylamine/ketone/aldehyde reaction products Dark brown solids Melt Point 85-95.degree. C. Specific Gravity 1.15General purpose antioxidants. TRADE NAME SUPPLIER__________________________________________________________________________ BXA-G Uniroyal Naugard BG Uniroyal Vanox AT Vanderbilt__________________________________________________________________________7. Substituted diphenylamine-structure not revealed Off-white powder Melt point 96-99.degree. C. Specific Gravity 1.14Non-discoloring amine antioxidant for polymers and plastics. TRADE NAME SUPPLIER__________________________________________________________________________ Naugard 445 Uniroyal__________________________________________________________________________
__________________________________________________________________________p-PHENYLENEDIAMINES__________________________________________________________________________1. NPhenyl-N'(1,3-dimethylbutyl)p-phenylenediamine ##STR69##Powerful and persistent antioxidant, flex crack inhibitor andantiozonant.TRADE NAME SUPPLIER__________________________________________________________________________WINGSTAY 300 GOODYEARAkrochem Antiozonant PD #2 Akron ChemAnto 3E PennwaltAntozite 67 VanderbiltAntozite 67F (1) VanderbiltFlexzone 7F, (1) UniroyalFlexzone 7L UniroyalPermanax 6PPD VulnaxSantoflex 13 MonsantoSantoflex 13F, (1) MonsantoUOP 588 UOPVulkanox 4020 MobayVulkanox 4020 Flake (1) Mobay__________________________________________________________________________ (1) Flaked form
2. NPhenyl-N'isopropyl-p-phenylenediamine ##STR70##Powerful antioxidant-antiozonant.TRADE NAME SUPPLIER__________________________________________________________________________Akrochem Antiozonant PD #1 Akron ChemAnto 3H PennwaltFlexzone 3C UniroyalPermanax IPPD VulnaxSantoflex IP MonsantoVulkanox 4010NA Mobay__________________________________________________________________________3. NPhenyl-N'(1-methylheptyl)-p-phenylenediamine ##STR71##Antioxidant-antiozonant. TRADE NAME SUPPLIER__________________________________________________________________________ UOP 688 UOP__________________________________________________________________________4. NPhenyl-N'cyclohexyl-p-phenylenediamine ##STR72##Antioxidant-antiozonant. TRADE NAME SUPPLIER__________________________________________________________________________ Flexzone 6H Uniroyal__________________________________________________________________________5. Mixed diaryl-p-phenylenediamines ##STR73##Persistent antioxidants, antiozonants and antiflex agents for manynatural and syntheticrubber compounds. Very powerful antiozonants for CR. Very non-volatileand slow toextract. PHYSICAL MELT SPECIFICTRADE NAME FORM POINT GRAVITY SUPPLIER__________________________________________________________________________WINGSTAY 100 Silver-gray flakes 90-105.degree. C. 1.18 GOODYEARWINGSTAY 100AZ Gray flakes 110.degree. C. 1.18 GOODYEAR(1)WINGSTAY 200 Low-melting 60.degree. C. 1.18 GOODYEAR semi-solid__________________________________________________________________________ (1) Special low scorch grade for neoprene (CR)6. N,N'Diphenyl-p-phenylenediamine ##STR74##General purpose antioxidant and flex crack inhibitor. Limited solubilityin most polymers. TRADE NAME SUPPLIER__________________________________________________________________________ Agerite DPPD Vanderbilt J-Z-F Uniroyal Naugard J Uniroyal Permanax DPPD Vulnax__________________________________________________________________________7. N,N'Di-beta-naphthyl-p-phenylenediamine ##STR75##Antioxidant and metal deactivator. Not an antiozonant. TRADE NAME SUPPLIER__________________________________________________________________________ Agerite White Vanderbilt Agerite White White (1) Vanderbilt__________________________________________________________________________ (1) Special grade
8. N,N'Bis(1,4-dimethylpentyl)-p-phenylenediamine ##STR76##General purpose antiozonant. Activates cure systems. TRADE NAME SUPPLIER__________________________________________________________________________ Flexzone 4L Uniroyal Santoflex 77 Monsanto UOP 788 UOP__________________________________________________________________________9. N,N'Bis(1-ethyl-3-methylpentyl)-p-phenylenediamine ##STR77##General purpose antiozonant. Activates cure systems. TRADE NAME SUPPLIER__________________________________________________________________________ Antozite 2 Vanderbilt Flexzone 8L Uniroyal UOP 88 UOP__________________________________________________________________________10. N,N'Bis(1-methylheptyl)-p-phenylenediamine ##STR78##General purpose antiozonant. Activates cure systems. TRADE NAME SUPPLIER__________________________________________________________________________ Antozite 1 Vanderbilt Santoflex 217 Monsanto UOP 288 UOP__________________________________________________________________________11. NPhenyl-N'-(p-toluenesulfonyl)-p-phenylenediamine ##STR79##Semi-discoloring antioxidant and copper inhibitor. TRADE NAME SUPPLIER__________________________________________________________________________ Aranox Uniroyal__________________________________________________________________________
______________________________________QUINOLINES______________________________________1. Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline ##STR80##General purpose semi-staining antioxidant used in dry rubber andlatex compounding. Used to impart high temperature resistance.Functions As a mild antiozonant. Specific Gravity 1.04-1.08 MELTTRADE NAME PHYS FORM POINT SUPPLIER______________________________________Agerite MA Tan powder 74.degree. C. Min. VanderbiltAgerite ME Pellets Tan pellets 74.degree. C. Min. VanderbiltAgerite PE Pellets Amber pellets 88.degree. C. Min. VanderbiltAgerite Resin D Amber pellets 74.degree. C. Min. VanderbiltAgerite Resin D Amber powder 74.degree. C. Min. VanderbiltPowderAkrochem Amber powder 75.degree. C. Min. AkronAntioxidant DQ ChemicalCyanox 12 Tan powder 75-110.degree. C. Cyanamid or flakesFlectol H Tan powder 75-110.degree. C. MonsantoLowinox ACP LowiNaugard Q Amber powder 75.degree. C. Min. UniroyalPennox HR Flake Tan flake 75-110.degree. C. PennwaltPennox HR Powder Tan powder 75-110.degree. C. PennwaltPermanax TQ Brown flake 79.degree. C. Min. VulnaxVulkanox HS Amber pellets 75.degree. C. Mobay______________________________________2. 6-Dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline ##STR81##General purpose antioxidant. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Santoflex DD Dark liquid 0.90-0.96 Monsanto______________________________________3. 6-Ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline ##STR82##Highly staining antioxidant and antiozonant. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Santoflex AW Dark liquid 1.02-1.05 MonsantoVulkanox EC Dark liquid 1.02-1.05 Mobay______________________________________
______________________________________BLENDED AMINES______________________________________1. 65% Dioctylated diphenylamine (J-2) and 35% N,N'--diphenyl-p-phenylenediamine (K-6)Antioxidant and flex cracking inhibitor. Melt Point 80-100.degree. C. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Agerite HP-S Black powder 1.11 VanderbiltAgerite HP-S Black Rodform 1.11 VanderbiltRodform______________________________________2. 50% Octylated diphenylamine (J-2), 25% N,N'--diphenyl-p-phenylenediamine (K-6) and 25% high temperature reaction productof diphenylamine and acetone. (J-4)Antioxidant and flex cracking inhibitor. Melt Point 70.degree. C. Min. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Agerite Hipar T Brown powder 1.15 Vanderbilt______________________________________3. 65% Diarylamine/ketone reaction product and35% N,N'--diphenyl-p-phenylenediamine (K-6)Antioxidant, flex cracking inhibitor and metal deactivator. Melt Point 87-99.degree. C. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Flexamine Brown powder 1.17 UniroyalFlexamine G Brown granules 1.17 Uniroyal______________________________________4. p-Phenylenediamine antiozonant blends-undisclosed composition.TRADE NAME PHYS FORM SUPPLIER______________________________________Flexzone 10L Dark liquid UniroyalFlexzone 11L Dark liquid UniroyalFlexzone 12L Dark liquid UniroyalFlexzone 15L Dark liquid UniroyalSantoflex 134 Dark liquid MonsantoUOP 57 (1) Dark liquid UOPUOP 62 (2) Dark liquid UOPUOP 256 (3) Dark liquid UOP______________________________________ (1) Blend of UOP 588 and UOP 788 (2) Blend of UOP 288 and UOP 688 (3) Blend of UOP 288, UOP 588 and UOP 688
5. Blend of 50% N,N'--bis(1,4-dimethylpentyl)-p-phenylenediamine(K-8) and 50% N--phenyl-N'--(1,3-dimethylbutyl)-p-phenylenediamine (K-1)General purpose antiozonant blend.TRADE NAME PHYS FORM SUPPLIER______________________________________Flexzone 9L Dark liquid Uniroyal______________________________________6. Antidegradant blends-undisclosed composition.General purpose antidegradant which may or may not bean antiozonant. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Naugard 477 Brown powder 1.18 UniroyalPermanax CR Brown granules 1.14 Vulnax______________________________________7. Antidegradant blendsGeneral purpose antidegradants. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Santoflex LC (1) Dark liquid 1.023 MonsantoSantoflex 134D (2) Dark liquid 0.96 MonsantoSantoflex 715 (3) Dark liquid 0.98 Monsanto______________________________________ (1) 1 Part N--(1,3dimethylbutyl)-N'--phenyl-p-phenylenediamine (K1), 1 part N--(1,4dimethylpentyl)-N'--phenyl-p-phenylenediamine and 4 parts 6ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (L3) (2) 162/3% N--(1,3Dimethylbutyl)-N'--phenyl-p-phenylenediamine (K1), 331/3% N--(1,4dimethylpentyl)-N'-- phenyl-p-phenylenediamine and 50% 6dodecyl-2,2,4-trimethyl-1,2 dihydroquinoline (L2) (3) 42% N--(1,3Dimethylbutyl)-N'--phenyl-p-phenylenediamine (K1), 42% N--(1,4dimethylpentyl)-N'--phenyl-p-phenylenediamine and 16% N,N'--bis(1,4dimethylpentyl)-p-phenylenediamine (K8)
8. Mixture of an alkylated mercaptobenzimidazole and an amineantioxidant SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Stangard 500 Tan powder 1.24 Harwick______________________________________9. Amine antioxidant blend-undisclosed composition SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Vanox 200 Brown liquid 1.13 VanderbiltVanox 200 Powder Brown powder 1.40 Vanderbilt______________________________________
______________________________________MISCELLANEOUS UNCLASSIFIEDANTIOXIDANTS AND ANTIOZONANTS______________________________________1. Nickel dibutyldithiocarbamate ##STR83##Antiozonant for SBR and NBR antioxidant for several specialty polymers. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Akrochem Nibud Green solid 1.27 Akron ChemicalNaugard NBC Green solid 1.27 UniroyalNBC Green solid 1.26 duPontVanox NBC Green solid 1.27 Vanderbilt______________________________________2. Nickel diisobutyldithiocarbamate ##STR84##Antiozonant for SBR and NBR; antioxidant for several specialty polymers. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Isobutyl Niclate Green powder 1.27 Vanderbilt______________________________________3. Nickel dimethyldithiocarbamate ##STR85##Specialty antioxidant and antiozonant. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Methyl Niclate Green powder 1.77 Vanderbilt______________________________________4. 3,9-Bis(3-cyclohexenyl)-2,4,8,10-tetraoxaspiro(5,5)undecaneNon-staining antiozonant. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________Vulkanox AFS/LG Gray powder 1.06 @ Mobay 90.degree. C.______________________________________5. Unsaturated acetal absorbed on clayNon-staining antiozonant. SPECIFICTRADE NAME PHYS FORM GRAVITY SUPPLIER______________________________________AkrochemAntiozonant E-9604 Gray powder 1.74 Akron Chemical______________________________________
The preceding listing of antioxidants is taken from a trade publication entitled: Index of Commercial Antioxidants & Antiozonants, 3rd Edition (1982), distributed by the Goodyear Chemicals division of Goodyear Tire and Rubber Co., Akron, Ohio. That publication does not recommend any of the listed antioxidants specifically for inclusion in polyvinyl chloride compositions, and only recommends the following antioxidants:
N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide);
N,N'-hexamethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide;
N-stearoyl-p-aminophenol; and
N-(4-hydroxyphenyl)stearamide;
specifically for inclusion in polyamides. (Many of the other listed antioxidants are recommended for inclusion in "plastics" without further definition of a composition.) This index does not suggest inclusion of antimicrobial materials in conjunction with the indicated antioxidants.
SUMMARY OF THE INVENTION
The essence of the present invention resides in the discovery that compositions and articles containing antimicrobial agents can be processed at relatively high temperatures, even when exposing a large surface area to the ambient atmosphere or other sources of oxygen (as when forming films or fibers), if the composition also contains an antioxidant (sometimes referred to herein as a "stabilizer"). Antioxidants have not previously been used to stabilize antimicrobial agents. Both the discovery of the nature of the oxidation problem and the discovery of its solution are facets of the present invention.
One aspect of the invention is an antimicrobial composition having improved resistance to degradation of antimicrobial activity as a result of exposure of said composition to heat. The composition comprises an antimicrobial agent and an antioxidant.
A second aspect of the invention is an unprocessed thermoplastic composition which will be resistant to microbial attack after being processed at an elevated temperature. This composition comprises a resin selected from the group consisting of polypropylene, polyamides, and polyvinyl chloride; an antimicrobial agent; and a amount of an antioxidant effective to reduce degradation of the antimicrobial agent while the composition is being melt processed.
A third aspect of the invention is an article, such as a film or fiber, having resistance to microbial attack. The article comprises a polymeric resin as described in the preceding paragraph, an antimicrobial agent, and an antioxidant. These components are combined to form a composition before the composition is melt processed to form the article.
Method aspects of the invention are also contemplated. One is a method for preserving the efficacy of an antimicrobial agent against heat-induced degradation, comprising the step of adding to the antimicrobial agent an effective amount of an antioxidant. Another is a method for melt processing a composition comprising a thermoplastic resin and an antimicrobial agent while maintaining the efficacy of the antimicrobial agent. This method comprises the steps of combining a thermoplastic resin, an antimicrobial agent, and an antioxidant, followed by melt processing the composition. "Melt processing" means the manipulation of the composition at an elevated temperature, which is typical when forming the composition into a useful article, particularly a fiber or film which has a large surface to volume ratio.
The compositions of the invention have a substantial advantage over unstabilized prior compositions. Either less of the antimicrobial agent can be used to provide a desired level of antimicrobial activity, or a given amount of the antimicrobial agent can provide greater activity.
DETAILED DESCRIPTION OF THE INVENTION
Compositions according to the present invention comprise one part by weight of an antimicrobial agent and from 0.1 to 50 parts, preferably from 1 to 5 parts by weight of an additive referred to here as a "stabilizer" which prevents thermal and oxidative degradation of the antimicrobial agent in the composition.
The contemplated antimicrobial agents stabilized according to the present invention include all those specified in the Background Art section, others known to those of ordinary skill in the art, and mixtures thereof. The preferred antimicrobial agents are as follows:
10,10'-oxybisphenoxarsine (OBPA);
10,10'-oxybisphenarsazine;
bis-n-tributyltin oxide;
zinc Omadine; and
N-(trichloromethylthio)cyclohexenedicarboxamide.
Broadly speaking, the stabilizers contemplated herein can be any material which is stable with respect to the selected antimicrobial agent and under melt processing conditions and which will protect the chosen antimicrobial agent against degradation due to exposure of the composition to heat and oxygen. Epoxidized soybean oil also has utility as an antioxidant.
The preferred antioxidants contemplated herein are selected from the group consisting of: hindered phenols (examples of which are 2,6-di-t-butyl-p-cresol or 2,6-di-t-butyl-4-methylphenol); polyphenols (an example of which is tetrakis(methylene-3-(3,5-di-t-butyl-4-hydroxyhydrocinnamate))methane, sold by Ciba-Geigy Corporation as Irganox 1010; phosphites (an example of which is tris-(2,4-di-t-butylphenyl)phosphite, sold by Ciba-Geigy Corporation, under the trade name Irgafos 168 and as a 1:1 mixture with N,N'-hexamethylene-bis-(3,5-di-t-butyl-4-hydroxyhydrocinnanamide) (Irganox 1098) under the trade name Irganox B 1171); thioesters (e.g. distearyl thiodipropionate); 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione; nickel bis(0-ethyl(3,5-di-t-butyl-4-hydroxylbenzyl)phosphonate; zinc 2-mercaptobenzimidazole; aromatic amines (such as N-phenyl-alpha-naphthylamine or alkylated diphenylamines); and combinations of the above.
The synergists contemplated herein are compounds which render the stabilizers more effective, typically by increasing the efficacy of the chosen stabilizer as an antioxidant for the antimicrobial compound. Two exemplary synergists are distearylthiodipropionate (DSTDP) and tris-(2,4-di-t-butylpheyl)phosphite. Other contemplated synergists, which also have utility as antioxidants, are the following compounds
2-mercapto-4-methylbenzimidazole;
2-mercapto-5-methylbenzimidazole;
zinc salt of 2-mercaptobenzimidazole;
2-mercaptotoluimidazole; and
zinc 2-mercaptotoluimidazole.
These are listed as compounds H-1 (2 entries), H-2, H-7, and H-8 in the preceding list of antioxidants. Other synergists known to the art are also contemplated for use herein.
A third ingredient contemplated within the scope of the present invention is a predominant proportion of a polymeric resin, optionally including the usual modifiers and process aids employed in the rubber and plastic formulation arts. Two resin compositions are particularly contemplated herein. First is a concentrate composition containing 1 to 80 percent (all numbers stated herein are by weight unless otherwise indicated) of an antimicrobial agent, a stabilizer, and enough of a polymeric resin to improve the dispersibility of the other ingredients. Second is a composition containing at least about 90% of the resin, preferably from 99 to about 99.99 percent of the resin, and a minor proportion of the antimicrobial agent and its stabilizer. The first composition has utility as a concentrated antimicrobial agent premix which can be readily and uniformly dispersed in a resin composition. The second composition has direct utility as a thermoplastic resin composition for fabrication into useful articles having antimicrobial protection. Other proportions of ingredients are also contemplated.
The resins contemplated for use herein are exemplified by the description in the Background Art section of the specification. Other resins not specified herein are also contemplated within the scope of the invention. The preferred resins are polyamides and polyvinyl chloride, which derive particular benefit from the invention because they are not conventionally compounded with resin antioxidants. Optional resin modifiers contemplated herein include plasticizers; extenders; stabilizers to deter degradation caused by environmental heat and light; fillers; dyes and pigments; flame retardants; lubricants; blowing agents; and so forth. The additives chosen for a particular composition are determined by the desired properties of the final composition. The range of possible additives is limited only by the need to ensure compatibility of all the components of the final composition.
The desired concentrations of the antimicrobial agent and additives in resin compositions are a complex function of the inherent activity of the agent, the tendency toward thermal degradation in other ingredients such as the resin, and the temperature and duration of fabrication. Generally the amount of additive desired is from 0.1 to 50 times, and preferably from about one to about five times the amount of the antimicrobial agent, and the active antimicrobial agent desirably comprises from 0.005% (50 ppm) to 1.0% (10,000 ppm) by weight of the thermoplastic composition. One exemplary unprocessed thermoplastic composition according to the present invention contains from about 170 to about 450 ppm (preferably 220 ppm) of the selected antimicrobial agent and enough of the selected antioxidant that, following heat processing, at least 100 ppm of the active antimicrobial agent will remain. Another exemplary unprocessed thermoplastic composition according to the present invention contains from about 85 to about 220 ppm of the selected antimicrobial agent, and enough of the chosen antioxidant that, after heat processing, at least 50 ppm of the active antimicrobial agent will remain.
It will be appreciated that the ratio: ##EQU1## will depend on the selection of the antimicrobial agent, the identity and amount of the resin and modifiers selected, the processing conditions, and other factors, so no universal ratio can be stated. However, inclusion of an effective antioxidant will always bring the above-stated ratio nearer to its ideal value of 1.0.
In the preferred OBPA composition containing nylon, OBPA, and an amount of an antioxidant sufficient to provide protection during heat processing, the ratio of initial OBPA to final OBPA is about 0.60. Thus, if at least about 100 ppm of OBPA is desired in a fiber, about 170 ppm to about 450 ppm of OBPA is incorporated in the original composition. (If the antioxidant were absent, a final effective level of 100 ppm in nylon fibers would require incorporation of about 500 ppm--three times the level of addition required if the present invention is practiced.) If at least about 50 ppm of OBPA is desired in a fiber, from about 85 to about 220 ppm of OBPA and an effective amount of an antioxidant are incorporated in the composition.
A preferred method for preparing the stabilized plastic compounds is to prepare a blend of the selected resin and antimicrobial agent in which the antimicrobial agent is included in a concentrate as described by Rei in U.S. Pat. No. 4,086,297. The patent is hereby incorporated herein by reference. The blend is then mixed with the desired resin and modifiers.
Compositions specifically contemplated for use herein include those comprising polycaprolactam resin, OBPA as an antimicrobial agent, and a phosphite stabilizer. Nylon is selected because of its desirable properties as a fiber, particularly as a carpet fiber. Nylon fibers are also formed at a high temperature, for example about 285.degree. C. for Nylon 6 (300.degree. C. for Nylon 6,6), and thus antimicrobial agents contained in nylon compositions have previously been substantially or completely inactivated during processing. OBPA is selected because it has a high level of antimicrobial activity, particularly when it is stabilized as taught herein. Phosphite stabilizers are selected because they can protect the microbial agent at the relatively high processing temperature used when fabricating nylon fibers.
Practice of the method inventions taught herein is described or self-evident from the preceding composition description and following examples.

EXAMPLES 1-6
Nylon 6 (polycaprolactam) chips were mixed with processing additives as defined below and with a concentrate of an antimicrobial agent previously prepared according to U.S. Pat. No. 4,086,297 (Rei) to achieve the blend compositions shown
TABLE I______________________________________Example 1 2 3______________________________________Polycaprolactam 99.95% 96.55% 93.45%(fiber grade)OBPA 0.05 0.05 0.05Tinuvin 234 -- 1.5 1.5Distearylthio- -- 0.4 0.4dipropionateIrganox 1098 -- -- --Irganox B1171 -- -- --Irganox 1010 -- 1.5 --Irganox B215 -- -- 4.5Nickel dithio- -- -- --carbamateMineral oil -- -- 0.1______________________________________Example 4 5 6______________________________________Polycaprolactam 96.45% 94.95% 96.45%(fiber grade)OBPA 0.05 0.05 0.05Tinuvin 234 1.5 1.5 1.5Distearylthio- 0.4 0.4 0.4dipropionateIrganox 1098 1.5 -- --Irganox B1171 -- 3.0 --Irganox 1010 -- -- --Irganox B215 -- -- --Nickel dithio- -- -- 1.5carbamateMineral Oil 0.1 0.1 0.1______________________________________
The blend compositions were each extruded into strands approximately 1/16 inch in diameter, cooled in a water bath, and immediately cut into pellets 1/8 inch long. These pellets were then melt-spun into nylon fibers according to techniques commonly known in the industry. The maximum processing temperature was about 285 degrees Celsius.
The fibers were subsequently evaluated for their biological activity by placing each one on a microbiological growth medium, solidified with agar, which had previously been innoculated with an actively growing culture of Staphylococcus aureus.
After incubating the media for 24 hours, the biological activity of each fiber sample was evaluated by measuring the width of the region around the fibers on the agar surface where no visible bacterial growth was evident. This width is defined as a Zone of Inhibition. Another evaluation of biological activity was made by extracting a specimen of each of the test samples with methanol. The extracted material was assayed by high performance liquid chromatography for recovery of the active antimicrobial agent. These results are tabulated in Table II.
TABLE II______________________________________ Zone of OBPAExample Inhibition (mm) % recovered______________________________________1 3 112 5 593 7 524 6 695 5 596 5 58______________________________________
It will be evident to those skilled in the art that the optimum treatment need not result in 100% recovery of OBPA, since it is added at a very low level and may be unavailable for analysis as the result of incomplete extraction.
These examples show that more undegraded OBPA remains in processed compositions 2-6 which also contain a stabilizing agent, and that the stabilized OBPA of Examples 2-6 is much more microbiocidally active than unstabilized OBPA of Example 1. (It should be understood that the Zone of Inhibition Test is conservative and underestimates the advantage of employing an antioxidant.)
The advantages of the higher active level of an antimicrobial agent resulting from stabilization will be evident to those skilled in the art. For one thing the stabilized fibers can be subjected to a greater amount of post-finishing than unstabilized compositions without reducing the amount or potency of the antimicrobial agent in the fiber when it is put into use.
EXAMPLES 7-10
Unstabilized powdered polypropylene (sold under the trademark Profax 6301 PM by Hercules, Inc., Wilmington, Del.) was mixed with OBPA prepared according to U.S. Pat. No. 4,086,297 and processing additives as follows:
TABLE III______________________________________Example 7 8 9 10______________________________________Polypropylene 99.95 98.70 97.95 96.95(Profax 6301)OBPA 0.05 0.05 0.05 0.05Irganox 1010 -- 1.0 1.0 1.0Distearylthio- -- 0.25 -- --dipropionateTinuvin 770 -- -- 1.0 2.0______________________________________
The blends were converted into pellets by melt extrusion as in the previous examples. These pellets were melt-spun into polypropylene fibers according to techniques commonly known to the industry.
Microbiological effectiveness and active ingredient levels were obtained as in the previous examples and the results are presented in Table IV.
TABLE IV______________________________________ OBPAExample Zone of Inhibition (mm) % Recovered______________________________________7 0 388 7 529 7 5910 6 58______________________________________
Again, the fibers of Examples 8-10, which contain a stabilizer for the antimicrobial agent, contain more extractable antimicrobial agent and provide a much greater zone of inhibition than the fiber of Example 7 which contains no stabilizer.
EXAMPLE 11
In this example a polyvinyl chloride film composition containing stabilized OBPA is formed using conventional technology.
The formulation of the base film is:
TABLE V______________________________________Component Weight (g)______________________________________Polyvinyl chloride resin 100.00Di-2-ethylexyl phthalate (DOP) 40.00Epoxidized soybean oil 7.70UV Stabilizer (Mark 202A) 1.00Heat Stabilizer (Mark KCB) 3.50Heat Stabilizer (Mark C) 1.50Stearic Acid 0.25OBPA concentrate* .05______________________________________ *expressed as amount of pure OBPA ("Mark" is a trademark for heat and light stabilizers sold by Argus Chemical Corp., Brooklyn, New York. DOP is a plasticizer, stearic acid is a lubricant, and epoxidized soybean oil is an antioxidant.)
Films are prepared by milling the components of the base until a uniform dispersion is obtained, at which time 0.05% by weight of carbon black is added.
The film is extrusion cast using conventional equipment at a processing temperature of 375 degrees Fahrenheit (191 degrees Celsius). The final film has a thickness of about 20 mils (500 microns). A control film is made in the same manner except that the stabilizer is omitted. The microbiocidal activity of the film is measured by cutting small round pieces of the test and control films, placing each one on an innoculated growth medium as described in Examples 1-6, and proceeding as described in those examples to develop and measure a Zone of Inhibition. The test samples are then extracted with methanol and the amount of recovered active ingredient is measured as described in Examples 1-6. Results comparable to those set forth in Examples 1-6 are obtained, illustrating that the invention can be used to improve antimicrobial films.
EXAMPLE 12
Examples 1 and 2 are repeated, except the OBPA is replaced in separate trials by each of the antimicrobial agents specified in the Background Art section of the present specification. The compositions analogous to Example 2 show much greater antimicrobial activity and a much greater recovery of the active antimicrobial agent than the corresponding compositions analogous to Example 1. This illustrates the applicability of the invention to each of the named antimicrobial agents.
EXAMPLE 13
Examples 1 and 2 are repeated, except the antioxidant (Irganox 1010) of Example 2 is replaced, in separate trials, by each of the antioxidants set forth in the Background Art section of the present specification. The compositions analogous to Example 2 show much greater antimicrobial activity and a much greater recovery of the active antimicrobial agent than the corresponding compositions analogous to Example 1. Thus, a wide range of antioxidants can be used to practice the invention.
EXAMPLE 14
Examples 1 and 2 are repeated, replacing polycaprolactam with each of the resins specified in the Background Art section of the present application in separate trials. Similar results are again obtained, and show the value of the invention for improving the antimicrobial properties of many different resin compositions.
EXAMPLE 15
The following test composition was blended and formed into test fibers according to the procedure described in Examples 1-6:
______________________________________Ingredient Wt. %______________________________________polycaprolactam 98.96Irganox B1171 0.50Tinuvin T234 0.50OBPA 0.04Total 100.00______________________________________
The fibers were then subjected to a modified continuous dyeing process adapted to simulate commercial continuous dyeing processes. The fibers were wet with a 0.1% by weight aqueous solution of a nonionic surfactant sold under the trademark Alrowet by Ciba-Geigy Corporation, Dyestuffs and Chemicals Division, Greensboro N.C.; followed by an aliquot of an aqueous solution adjusted to a pH value of 6.0 and containing 0.1% of the same surfactant and 2% of a dye sold under the trademark "Tectilon Blue 4RKWL" by Ciba-Geigy Corporation, Dyestuffs and Chemicals Division, Greensboro, N.C. The saturated fibers were steamed for 360 seconds at 101.degree. C. and atmospheric pressure, followed by three rinses, each one liter of 40.degree. C. tap water.
Fibers so treated were found to have retained all of their antimicrobial potency and 76% of their OBPA, as measured by high performance liquid chromatography.
EXAMPLE 16
Test fibers like those of Example 15 were used again here. A control composition lacking Irganox B1171 antioxidant but otherwise containing the same ingredients in the same proportions was processed in the same manner, then formed into control fibers.
The test and control fibers were then subjected to Beck mock-dyeing. Mock dye baths were prepared having a pH of 4.0 and containing 0.1% Triton X-100 surfactant in aqueous solution. In separate trials, 5% and 10% (based on the weight of the dye bath) of the test and control fibers were added to the boiling dye baths. The dye baths were boiled for up to 30 minutes.
The baths were then analyzed for arsenic content. The baths used to boil the control fibers contained about three times as much arsenic as the corresponding baths used to boil the test fibers containing an antioxidant. Thus, use of an antioxidant to preserve an antimicrobial agent in these fiber compositions reduces the loss of decomposition products of the antimicrobial agent into the dye bath, and thus into the dye effluent.

Claims

1. A thermoplastic composition which will be resistant to microbial attack after being processed at an elevated temperature, comprising a homogeneous mixture of:
A. a polyamide resin;
B. an antimicrobial agent; and
C. an amount of an antioxidant effective to reduce degradation of said antimicrobial agent while said composition is being melt-processed.
2. The composition of claim 1, wherein said antioxidant is at least one member selected from the group consisting of:
monophenols;
bisphenols
thiobisphenols;
polyphenols;
hydroquinones;
phosphites;
thioesters;
naphthylamines;
diarylamines;
p-phenylenediamines;
quinolines;
blended amines;
0,0-di-n-octadecyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate);
1,6-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamate);
1,6-hexamethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate);
thiodiethylene bis(3,5-di-t-butyl-4-hydroxy)hydrocinnamate;
thiodiethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate);
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate;
octadecyl-3,5-di-t-butyl-4-hydroxyhydrocinnamate;
3.
3. 5-di-t-butyl-4-hydroxyhydrocinnamic acid triester with 1,3,5-tris (2-hydroxyethyl)-s-triazine-2,4,6-(1H,3H,5H)trione;
N-butyryl-p-aminophenol;
N-(4-hydroxyphenyl)butyramide;
N-pelargonoyl-p-aminophenol;
N-(4-hydroxyphenyl)pelargonamide;
N-lauroyl-p-aminophenol;
N-(4-hydroxyphenyl)dodecanamide;
2,6-di-t-butyl-alpha-dimethylamino-p-cresol;
2,6-di-t-butyl-4-(dimethylaminomethyl)phenol;
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione;
nickel bis(0-ethyl(3,5-di-butyl-4-hydroxybenzyl)phosphonate);
2,2'-oxamidobisethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate;
tris(2-t-butyl-4-(2-methyl-4-hydroxy-5-t-butylphenylthio)-5-methyl)-phenylphosphite;
bis(3,3-bis(4-hydroxy-3-t-butylphenyl)butanoic acid glycolester;
tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylylenediphosphonite;
n-propyl gallate;
n-propyl-3,4,5-trihydroxybenzoate;
calcium bis(0-ethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate);
2-mercapto-4-methylbenzimidazole;
2-mercapto-5-methylbenzimidadole;
zinc salt of 2-mercaptobenzimidazole;
2-mercapto-4-methylbenzimidazole, zinc salt;
2-mercapto-5-methylbenzimidazole, zinc salt;
2-mercaptotoluimidazole;
zinc 2-mercaptotoluimidazole;
dioctadecyl disulfide;
metal aromatic sulfonates;
nickel di-n-butyldithiocarbamate;
nickel diisobutyldithiocarbamate;
nickel dimethyldithiocarbamate;
3,9-bis(3-cyclohexenyl)-2,4,8,10-tetraoxaspiro(5,5)undecane; and
tris (5-norbornene-2-methyl)phosphite. 3. The composition of claim 1, wherein said antioxidant is 2,6-di-t-butyl-p-cresol.
4. The composition of claim 1, wherein said antioxidant is 2,6-di-t-butyl-4-methylphenol.
5. The composition of claim 1, wherein said antioxidant is tetrakis(methylene-3-(3,5-di-t-butyl-4-hydroxyhydrocinnamate))methane.
6. The composition of claim 1, wherein said antioxidant is tris-(2,4-di-t-butylphenyl)phosphite.
7. The composition of claim 1, wherein said antioxidant is distearyl thiodipropionate.
8. The composition of claim 1, wherein said antioxidant is 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione.
9. The composition of claim 1 wherein said antioxidant is nickel bis(O-ethyl(3,5-di-t-butyl-4-hydroxylbenzyl)phosphonate).
10. The composition of claim 1, wherein said antioxidant is zinc 2-mercaptobenzimidazole.
11. The composition of claim 1, wherein said antioxidant is N-phenyl-alpha-naphthylamine.
12. The composition of claim 1, wherein said antioxidant is an alkylated diphenylamine.
13. The composition of claim 1, wherein said antioxidant is N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide).
14. The composition of claim 1, wherein said antioxidant is N,N'-hexamethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide.
15. The composition of claim 1, wherein said antioxidant is 1,6-hexamethylene bis-(3,5-di-t-butyl-4-hydroxyhydrocinnamide).
16. The composition of claim 1, wherein said antioxidant is tetrakis(methylene 3,5-di-t-butyl-4-hydroxyphenyl propionate)methane.
17. The composition of claim 1, wherein said antioxidant is tetrakis(methylene-3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane.
18. The composition of claim 1, wherein said antioxidant is nickel dithiocarbamate.
19. The composition of claim 1, wherein said resin is polycaprolactam.
20. The composition of claim 1, wherein said antimicrobial agent comprises from about 170 to about 450 ppm of 10,10'-oxybisphenoxarsine, and provides an active level of 10,10'-oxybisphenoxarsine of at least about 100 ppm after said processing at an elevated temperature.
21. The composition of claim 1, wherein said antimicrobial agent comprises from about 85 to about 220 ppm of 10,10'-oxybisphenoxarsine, and provides an active level of 10,10'-oxybisphenoxarsine of at least 50 ppm after said processing at an elevated temperature.
22. The composition of claim 20, wherein said antimicrobial agent comprises about 170 ppm thereof.
23. The composition of claim 20, wherein said antimicrobial agent comprises about 200 ppm thereof.
24. The composition of claim 1, wherein said antimicrobial agent is 10,10'-oxybisphenoxarsine, said antioxidant is at least one member selected from the group consisting of:
distearyldithiopropionate;
N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide);
N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamide);
1,6-hexamethylene bis-(3,5-di-t-butyl-4hydroxyhydrocinnamide);
tris-(2,4-di-t-butylphenyl)phosphite;
tetrakis(methylene-3-(3,5-di-t-butyl-4-hydroxyhydrocinnamate))methane; and
nickel dithiocarbamate;
and said resin is polycaprolactam.
25. The composition of claim 24, wherein said 10,10'-oxybisphenoxarsine comprises from about 170 to about 450 ppm thereof, and provides an active level of said 10,10'-oxybisphenoxarsine of at least about 100 ppm after said processing at an elevated temperature.
26. The composition of claim 24, wherein said 10,10'-oxybisphenoxarsine comprises from about 85 to about 220 ppm thereof and provides an active level of said 10,10'-oxybisphenoxarsine of at least 50 ppm after said processing at an elevated temperature.
27. The composition of claim 24, wherein said 10,10'-oxybisphenoxarsine comprises about 170 ppm thereof.
28. The composition of claim 24, wherein said 10,10'-oxybisphenoxarsine comprises about 200 ppm thereof.
29. An article selected from the group consisting of fibers and films, said article having resistance to microbial attack, said article comprising a homogeneous mixture of:
A. a polyamide resin;
B. an antimicrobial agent; and
C. an antioxidant;
wherein said ingredients A, B, and C are combined to form a composition before said composition is melt-processed to form said article.
30. The article of claiim 29, wherein said antioxidant is at least one member selected from the group consisting of:
monophenols;
bisphenols;
thiobisphenols;
polyphenols;
hydroquinones;
phosphites;
thioesters;
naphthylamines;
diarylamines;
p-phenylenediamines;
quinolines;
blended amines;
O,O-di-n-octadecyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate;
1. 6-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamate;
1,6-hexamethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate);
thiodiethylene bis(3,5-di-t-butyl-4-hydroxy)hydrocinnamate;
thiodiethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate);
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate;
octadecyl-3,5-di-t-butyl-4-hydroxyhydrocinnamate;
3,5-di-t-butyl-4-hydroxyhydrocinnamic acid triester with 1,3,5-tris(2-hydroxyethyl)-s-triazine-2,4,6-(1H,3H,5H)trione;
N-butyryl-p-aminophenol;
N-(4-hydroxyphenyl)butyramide;
N-pelargonoyl-p-aminophenol;
N-(4-hydroxyphenyl)pelargonamide;
N-lauroyl-p-aminophenol;
N-(4-hydroxyphenyl)dodecanamide;
2,6-di-t-butyl-alpha-dimethylamino-p-cresol;
2,6-di-t-butyl-4-(dimethylaminomethyl)phenol;
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione;
nickel bis(0-ethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate);
2. 2'-oxamidobisethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate;
tris(2-t-butyl-4-(2-methyl-4-hydroxy-5-t-butylphenylthio)-5-methyl)-phenylphosphite;
bis(3,3-bis(4-hydroxy-3-t-butylphenyl)butanoic acid glycolester;
tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylylenediphosphonite;
n-propyl gallate;
n-propyl-3,4,5-trihydroxybenzoate;
calcium bis(0-ethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate);
2-mercapto-4-methylbenzimidazole;
2-mercapto-5-methylbenzimidazole;
zinc salt of 2-mercaptobenzimidazole;
2-mercapto-4-methylbenzimidazole, zinc salt;
2-mercapto-5-methylbenzimidazole, zinc salt;
2-mercaptotoluimidazole;
zinc-2-mercaptotoluimidazole;
dioctadecyl disulfide;
metal aromatic sulfonates;
nickel di-n-butyldithiocarbamate;
nickel diisobutyldithiocarbamate;
nickel dimethyldithiocarbamate;
3,9-bis(3-cyclohexenyl)-2,4,8,10-tetraoxaspiro(5,5)undecane; and
tris(5-norbornene-2-methyl)phosphite.
31. The article of claim 30, wherein said resin is polycaprolactam.
32. The article of claim 29, wherein said antimicrobial agent is 10,10'-oxybisphenoxarsine, said antioxidant is at least one member selected from the group consisting of:
distearyldithiopropionate;
N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide);
N,N'-hexamethylene bis(3-(3,5-di-t-butyl 4-hydroxyphenyl)propionamide);
1,6-hexamethylene bis-(3,5-di-t-butyl-4-hydroxyhydrocinnamide);
tris-2(2,4-di-t-butylphenyl)phosphite;
tetrakis(methylene-3-(3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane; and
nickel dithiocarbamate;
and said resin is polycaprolactam.
33. The composition of claim 1, wherein the weight ratio of said antimicrobial agent to said stabilizer is from about 1:1 to about 1:5.
34. The composition of claim 24, wherein the weight ratio of said antimicrobial agent to said stabilizer is from about 1:1 to about 1:5.
35. A thermoplastic composition which will be resistant to microbial attack after being processed at an elevated temperature, comprising a homogeneous mixture of:
A. a resin selected from the group consisting of polypropylene, polyamide, and polyvinyl chloride;
B. an antimicrobial agent; and
C. an amount of an antioxidant effective to reduce degradation of said antimicrobial agent while said composition is being melt processed, wherein said antioxidant is at least one member selected from the group consisting of:
hydroquinones;
thioesters;
naphthylamines;
diarylamines;
p-phenylenediamines;
quinolines;
blended amines;
tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylylenediphosphonite;
2-mercapto-4-methylbenzimidazole;
2-mercapto-5-methylbenzimidazole;
zinc salt of 2-mercaptobenzimidazole;
2-mercapto-4-methylbenzimidazole, zinc salt;
2-mercapto-5-methylbenzimidazole, zinc salt;
2-mercaptotoluimidazole;
zinc 2-mercaptotoluimidazole;
dioctadecyl disulfide;
metal aromatic sulfonates;
nickel di-n-butyldithiocarbamate;
nickel diisobutyldithiocarbamate;
nickel dimethyldithiocarbamate; and
3,9-bis(3-cyclohexenyl)-2,4,8,10-tetraoxaspiro(5,5)undecane.
36. The composition of claim 35, wherein said antioxidant is distearyl thiodipropionate.
37. The composition of claim 35, wherein said antioxidant is zinc 2-mercaptobenzimidazole.
38. The composition of claim 35, wherein said antioxidant is N-phenyl-alpha-naphthylamine.
39. The composition of claim 35, wherein said antioxidant is an alkylated diphenylamine.
40. The composition of claim 35, wherein said antioxidant is nickel dithiocarbamate.
41. The composition of claim 35, wherein said resin is a polyamide.
42. The composition of claim 35, wherein said resin is polycaprolactam.
43. The composition of claim 35, wherein said antimicrobial agent comprises from about 170 to about 450 ppm of 10,10'-oxybisphenoxarsine, and provides an active level of 10,10'-oxybisphenoxarsine of at least about 100 ppm after said processing at an elevated temperature.
44. The composition of claim 43, wherein said antimicrobial agent comprises about 170 ppm thereof.
45. The composition of claim 43, wherein said antimicrobial agent comprises about 200 ppm thereof.
46. The composition of claim 35, wherein said antimicrobial agent comprises from about 85 to about 220 ppm of 10,10'-oxybisphenoxarsine, and provides an active level of 10,10'-oxybisphenoxarsine of at least 50 ppm after said processing at an elevated temperature.
47. The composition of claim 35, wherein the weight ratio of said antimicrobial agent to said stabilizer is from about 1:1 to about 1:5.
48. The composition of claim 35, wherein said antimicrobial agent is 10,10'-oxybisphenoxarsine, said antioxidant is at least one member selected from the group consisting of:
distearyldithiopropionate; and
nickel dithiocarbamate;
and said resin is polycaprolactam.
49. The composition of claim 48, wherein the weight ratio of said antimicrobial agent to said stabilizer is from about 1:1 to about 1:5.
50. An article selected from the group consisting of fibers and films, said article having resistance to microbial attack, said article comprising a homogeneous mixture of:
A. a polymeric resin selected from the group consisting of polyamides, polyvinyl chlorides and polypropylene;
B. an antimicrobial agent; and
C. an antioxidant;
wherein said ingredients A, B, and C are combined to form a composition before said composition is meltprocessed to form said article, and wherein said antioxidant is at least one member selected from the group consisting of:
hydroquinones;
thioesters;
naphthylamines;
diarylamines;
p-phenylenediamines;
quinolines;
blended amines;
tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylylenediphosphonite;
2-mercapto-4-methylbenzimidazole;
2-mercapto-5-methylbenzimidazole;
zinc salt of 2-mercaptobenzimidazole;
2-mercapto-4-methylbenzimidazole, zinc salt;
2-mercapto-5-methylbenzimidazole, zinc salt;
2-mercaptotoluimidazole;
zinc-2-mercaptotoluimidazole;
dioctadecyl disulfide
metal aromatic sulfonates;
nickel di-n-butyldithiocarbamate;
nickel diisobutyldithiocarbamate;
nickel dimethyldithiocarbamate; and
3,9-bis(3-cyclohexenyl)-2,4,8,10-tetraoxaspiro(5,5)undecane.
51. The article of claim 50, wherein said resin is a polyamide.
52. The article of claim 51, wherein said resin is polycaprolactam.
53. The article of claim 50, wherein said antimicrobial agent is 10,10'-oxybisphenoxarsine, said antioxidant is at least one member selected from the group consisting of:
distearyldithiopropionate; and
nickel dithiocarbamate;
and said resin is polycaprolactam.
54. A method for melt processing a composition comprising a thermoplastic resin and an antimicrobial agent while maintaining the efficacy of said agent, comprising the following steps performed in the order stated:
A. combining said thermoplastic resin, said antimicrobial agent, and an antioxidant to form a protected antimicrobial resin composition; and
B. melt processing said protected antimicrobial resin composition.
55. A method for providing a desired final active level of at least 1 part by weight of 10,10'-oxybisphenoxarsine in a composition following heat processing thereof, comprising the steps of:
A. providing a thermoplastic composition comprising a major proportion of a resin selected from the group consisting of polypropylene, polyamide, and polyvinyl chloride; about 1.7 parts by weight of 10,10'-oxybisphenoxarsine; and from about 1.7 to about 8.5 parts by weight of an antioxidant; and
B. processing said composition at a temperature of at lest about 275 degrees Celsius;
thereby providing a heat-processed composition containing at least about 1.0 parts by weight of said 10,10'-oxybisphenoxarsine in active form.
56. The method of claim 55, wherein said resin is a polyamide resin.
57. The method of claim 55, wherein said processing step is carried out by melt processing said thermoplastic composition to form an article selected from the group consisting of fibers and films.
58. The method of claim 57, comprising the subsequent step of vat dyeing said article.
59. The method of claim 58, wherein said article is a carpet fiber.
60. A method for melt-processing a composition comprising a thermoplastic polyamide resin and an antimicrobial agent while maintaining the efficacy of said agent, comprising the following steps performed in the order stated:
A. combining said thermoplastic polyamide resin, said antimicrobial agent, and an antioxidant homogeneously to form a protected antimicrobial resin composition; and
B. melt-processing said protected antimicrobial resin composition.
61. A method for providing a desired final active level of at least 1 part by weight of 10,10'-oxybisphenoxarsine in a composition following heat processing thereof, comprising the steps of:
A. providing a thermoplastic composition comprising about 1.7 parts by weight of 10,10'-oxybisphenoxarsine, from about 1.7 to about 8.5 parts by weight of an antioxidant, and a major proportion of a polyamide resin; and
B. processing said thermoplastic composition at a temperature of at least about 275 degreess Celsius;
thereby providing a heat-processed composition containing about 1.0 parts by weight of said 10,10'-oxybisphenoxarsine in active form.
62. The method of claim 61, wherein said processing step is carried out by melt processing said thermoplastic composition to form an article selected from the group consisting of fibers and films.
63. The method of claim 62, comprising the subsequent step of vat dyeing said article.
64. The method of claim 63, wherein said article is a carpet fiber.

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Entry
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Compositions containing antimicorbial agents in combination with stabilizers

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US Referenced Citations (13)

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