Plastic films, fibers and articles are provided long-term antimicrobial activity with a combination of certain phenolic and inorganic antimicrobial agents. The plastic films, fibers and articles with antimicrobial activity exhibit superior resistance to discoloration, may be processed at high temperature, and maintain physical properties upon weathering, especially upon exposure to ultraviolet radiation.

The present invention relates to combinations of phenolic and inorganic compounds which exhibit excellent antimicrobial activity when incorporated into a substrate resin, which mixtures do not exhibit the negative effects associated with the use of either alone. Plastic articles manufactured via a variety of processes from such resins are provided long term antimicrobial activity and exhibit superior resistance to discoloration and maintenance of physical properties, especially upon exposure to ultraviolet radiation.
Triclosan, or Irgaguard(copyright), Ciba Specialty Chemicals, 2,4,4xe2x80x2-trichloro-2xe2x80x2-hydroxydiphenyl ether, is a known antimicrobial for plastics applications. It is known to have high activity against numerous gram-positive and gram-negative bacterial. It can be incorporated as a neat material or via a masterbatch into a variety of polymer substrates, for example, polyethylenes such as LDPE, HDPE, MDPE, polypropylene (PP), acrylonitrile-butadiene-styrene terpolymer (ABS), styrene-acrylonitrile copolymer (SAN), polystyrene (PS), polyacrylates, polymethyl methacrylate (PMMA), polyamide, polyesters, polyvinyl chloride (PVC), polymer latex, polyurethane (PUR), thermoplastic polyurethane (TPU), unsaturated polyester (UP), urea formaldehyde resin (UF), etc. Irgaguard(copyright) exhibits high activity at the surface of plastic articles and the activity remains after repeated washing of plastic articles. Further, Irgaguard(copyright) has a good toxicological profile.
Disadvantages of Irgaguard(copyright) are that plastic articles formulated with it exhibit strong discloloration upon weathering. For example, polypropylene samples containing Irgaguard(copyright) exposed in a Xenon Arc Weather-Ometer at 035 W/m2, 63xc2x0 C. discolor within hours. Further, processing at temperatures greater than 250xc2x0 C. is poblematic due to the volatility of Irgaguard(copyright).
Silver based materials, such as colloidal silver, silver nitrate, silver sulfate, silver chloride, silver complexes and silver ion containing zeolites are known antimicrobial agents for plastic articles. Silver compounds exhibit high activity against microorganisms and they have a good toxicological profile. High processing temperatures are possible with silver compounds (greater than 300xc2x0 C.).
Disadvantages of silver based antimicrobials are that plastic articles containing them often exhibit discloloration upon weathering, and the activity on the surface of the articles is often lost after repeated washing.
It has been found, surprisingly, that a combination of certain phenolic compounds with certain inorganic compounds avoids the disadvantages of using either Irgaguard(copyright) or silver based antimicrobials alone in plastic articles while providing excellent long-term antimicrobial activity to the articles.
An object of the present invention is to provide a novel mixture of antimicrobial agents for plastics applications.
Another object of the invention is to provide plastic articles or films with antimicrobial activity which also exhibit superior resistance to discoloration, may be processed at high temperatures, and which maintain physical properties upon weathering, especially upon exposure to UV radiation.
The instant invention pertains to a novel mixture of antimicrobial agents for plastics applications which comprises
a) at least one phenolic antimicrobial compound, and
b) at least one inorganic antimicrobial compound,
wherein
the phenolic antimicrobial compound is of the formula (I)
wherein
n is 0 or 1,
R1 and R2 are hydrogen or chlorine,
R3 is hydrogen or hydroxyl,
R4, R5 and R6 are hydrogen or chlorine,
R7 is hydroxyl, and
X is xe2x80x94Oxe2x80x94 or xe2x80x94CH2xe2x80x94,
and wherein the inorganic antimicrobial compound is selected from the group consisting of zinc oxide, copper and copper compounds, colloidal silver, silver nitrate, silver sulphate, silver chloride, silver complexes, metal-containing zeolites and surface-modified metal-containing zeolites,
and wherein the ratio of components a):b) is from about 1:9 to about 9:1.
Preferred phenolic antimicrobial compounds of component a) are o-benzyl-phenol, 2-benzyl-4-chloro-phenol, 2,4,4xe2x80x2-trichloro-2xe2x80x2-hydroxydiphenyl ether, 4,4xe2x80x2-dichloro-2-hydroxydiphenyl ether, 5-chloro-2-hydroxy-diphenyl-methane, mono-chloro-o-benzyl-phenol, 2,2xe2x80x2-methylenbis-(4-chloro-phenol) and 2,4,6-trichlorophenol.
Most preferred phenolic antimicrobial compounds of component a) are 2,4,4xe2x80x2-trichloro-2xe2x80x2-hydroxydiphenyl ether and 4,4xe2x80x2-dichloro-2-hydroxydiphenyl ether.
The metal-containing zeolites of component b) are those such as described in U.S. Pat. Nos. 4,775,585, 4,911,898, 4,911,899 and 6,071,542, the disclosures of which are hereby incorporated by reference. A zeolite is generally aluminosilicate having a three dimensionally grown skeleton structure and is generally represented by xM2/nO.Al2O3.ySiO2.zH2O, written with Al2O3 as a basis, wherein M represents an ion-exchangeable metal ion, which is usually the ion of a monovalent or divalent metal; n corresponds to the valence of the metal; x is a coefficient of the metal oxide; y is a coefficient of silica; and z is the number of water of crystallization. The zeolites of the present invention have a specific surface area of at least 150 m2/g.
Antibacterial metals for use in metal-containing zeolites include silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium, cobalt, nickel, zirconium, or a combination of two or more of these metals. Preference is given to silver, copper, zinc and zirconium, or a combination of these. Especially preferred metals are silver alone or a combination of silver with copper, zinc or zirconium.
Particularly preferred inorganic antimicrobial compounds of component b) are surface-modified metal-containing zeolites according to U.S. Pat. No. 6,071,542.
Especially preferred is the antimicrobial mixture wherein component a) is 2,4,4xe2x80x2-trichloro-2xe2x80x2-hydroxydiphenyl ether and wherein the inorganic antimicrobial compound of component b) is a surface-modified silver-containing zeolite. The term xe2x80x9csilver-containingxe2x80x9d includes the combination of silver with other metals such as zinc, copper and zirconium. BACTEKILLER BM-102GA (Kanebo) is an example of a surface-modified silver-containing zeolite according to U.S. Pat. No. 6,071,542.
In addition to zeolites, it is also contemplated that antibacterial metals such as silver, silver compounds and silver complexes may be supported on other inert materials, for example SiO2, TiO2 and glass.
The instant invention also pertains to plastic films, fibers or articles that comprise the novel mixture of components a) and b).
The novel antimicrobial mixture of components a) and b) may be incorporated into the plastic resin prior to its being subjected to such manufacturing processes as blown film, rotational molding, fiber spinning, etc. The mixture of components a) and b) is able to withstand demanding processing conditions such as high temperature, e.g. temperatures greater than 200xc2x0 C.
The plastic films, fibers and articles comprising the present antimicrobial mixture of components a) and b) is suitable for outdoor exposure; they are resistant to weathering and UV light degradation.
The antimicrobial mixture of components a) and b) exhibit good long-term activity and a good toxicological profile.
Triclosan containing plastic samples lead to a strong discoloration within a very short time when exposed to weathering. Plastic samples containing the present combination of components a) and b) exhibit only minimal color changes.
Triclosan containing plastic samples exhibit a reduced light stability. Plastic samples containing the present combination of components a) and b) exhibit physical properties that are comparable to a control formulation without antimicrobial agents.
The plastic films, fibers and articles of the present invention are advantageously employed for applications that require long-term hygienic activity on the surface, e.g., medical devices, hand rails, door handles, etc. The antimicrobial plastic films, fibers and articles of the present invention are used for example in hospitals, households, public institutions, ventilation systems, air cleaning and air conditioning systems and waste disposal systems. Plastic articles exposed to outdoor weathering that may have incorporated therein the antimicrobial mixture of the present invention are for example waste containers, swimming pool equipment, outdoor swing set equipment, slides and the like, and stadium seats.
The plastic films, fibers and articles of the present invention exhibit high antimicrobial activity at the surface. The antimicrobial activity remains after repeated washings.
The plastic films, fibers and articles of the present invention, that is to say, the plastic materials, may also have incorporated therein one or more of the following known additives:
1. Antioxidants
1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(xcex1-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1-methylundec-1-yl)phenol, 2,4-dimethyl-6-(1-methylheptadec-1-yl)phenol, 2,4-dimethyl-6-(1-methyltridec-1-yl)phenol and mixtures thereof.
1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl4-nonylphenol.
1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
1.4. Tocopherols, for example xcex1-tocopherol, xcex2-tocopherol, xcex3-tocopherol, xcex4-tocopherol and mixtures thereof (Vitamin E).
1.5. Hydroxylated thiodiphenyl ethers, for example 2,2xe2x80x2-thiobis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-thiobis(4-octylphenol), 4,4xe2x80x2-thiobis(6-tert-butyl-3-methylphenol), 4,4xe2x80x2-thiobis(6-tert-butyl-2-methylphenol), 4,4xe2x80x2-thiobis-(3,6-di-sec-amylphenol), 4,4xe2x80x2-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.
1.6. Alkylidenebisphenols, for example 2,2xe2x80x2-methylenebis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-methylenebis(6-tert-butyl-4-ethylphenol), 2,2xe2x80x2-methylenebis[4-methyl-6-(xcex1-methylcyclohexyl)phenol], 2,2xe2x80x2-methylenebis(4-methyl-6-cyclohexylphenol), 2,2xe2x80x2-methylenebis(6-nonyl-4-methylphenol), 2,2xe2x80x2-methylenebis(4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidenebis(4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2xe2x80x2-methylenebis[6-(xcex1-methylbenzyl)-4-nonylphenol], 2,2xe2x80x2-methylenebis[6-(xcex1,xcex1-dimethylbenzyl)-4-nonylphenol], 4,4xe2x80x2-methylenebis(2,6-di-tert-butylphenol), 4,4xe2x80x2-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3xe2x80x2tert-butyl-2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
1.7. Benzyl compounds, for example 3,5,3xe2x80x2,5xe2x80x2-tetra-tert-butyl-4,4xe2x80x2-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester, bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester and 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester, calcium-salt.
1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-benzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.12. Acylaminophenols, for example 4-hydroxy-lauric acid anilide, 4-hydroxy-stearic acid anilide, 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine and octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.
1.13. Esters of xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of xcex2-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexane-diol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,Nxe2x80x2-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl-olpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.15. Esters of xcex2-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide. 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,Nxe2x80x2-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard(copyright)XL-1 supplied by Uniroyal).
1.18. Ascorbic acid (vitamin C)
1.19. Aminic antioxidants, for example N,Nxe2x80x2-di-isopropyl-p-phenylenediamine, N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, N,Nxe2x80x2-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-methylheptyl)-p-phenylenediamine, N,Nxe2x80x2-dicyclohexyl-p-phenylenediamine, N,Nxe2x80x2-diphenyl-p-phenylenediamine, N,Nxe2x80x2-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-Nxe2x80x2-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-Nxe2x80x2-phenyl-p-phenylenediamine, N-(1-methylheptyl)-Nxe2x80x2-phenyl-p-phenylenediamine, N-cyclohexyl-Nxe2x80x2phenyl-p-phenlenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,Nxe2x80x2-dimethyl-N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,pxe2x80x2-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4xe2x80x2-diaminodiphenylmethane, 4,4xe2x80x2-diaminodiphenylmethane, N,N,Nxe2x80x2,Nxe2x80x2-tetramethyl-4,4xe2x80x2-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1xe2x80x2,3xe2x80x2-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyl-diphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazin, N,N,Nxe2x80x2,Nxe2x80x2-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)-sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
2. UV Absorbers and Light Stabilizers
2.1. 2-(2-Hydroxyphenyl)-2H-benzotriazoles, for example known commercial hydroxyphenyl-2H-benzotriazoles and benzotriazoles as disclosed in, U.S. Pat. Nos. 3,004,896; 3,055,896; 3,072,585; 3,074,910; 3,189,615; 3,218,332; 3,230,194; 4,127,586; 4,226,763; 4,275,004; 4,278,589; 4,315,848; 4,347,180; 4,383,863; 4,675,352; 4,681,905, 4,853,471; 5,268,450; 5,278,314; 5,280,124; 5,319,091; 5,410,071; 5,436,349; 5,516,914; 5,554,760; 5,563,242; 5,574,166; 5,607,987 and 5,977,219, such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole, 5-chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole, 5-chloro-2-(3-t-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-sec-butyl-5-t-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3,5-bis-xcex1-cumyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-(xcfx89-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-, phenyl)-2H-benzotriazole, 2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonyl)ethylphenyl)-2H-benzotriazole, dodecylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole, 2-(3-t-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole, 2,2xe2x80x2-methylene-bis(4-t-octyl-(6-2H-benzotriazol-2-yl)phenol), 2-(2-hydroxy-3-xcex1-cumyl-5-t-octylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-t-octyl-5-xcex1-cumylphenyl)-2H-benzotriazole, 5-fluoro-2-(2-hydroxy-3,5-di-xcex1-cumyl-phenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3,5-di-xcex1-cumylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3-xcex1-cumyl-5-t-octylphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2--isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-xcex1-cumyl-5-t-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-octylphenyl)-2H-benzotriazole, methyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyhydrocinnamate, 5-butylsulfonyl-2-(2-hydroxy-3-xcex1-cumyl-5-t-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-xcex1-cumyl-5-t-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-xcex1-cumylphenyl)-2H-benzotriazole, 5-butylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole and 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2xe2x80x2,4xe2x80x2-trihydroxy and 2xe2x80x2-hydroxy-4,4xe2x80x2-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates and malonates, for example, xcex1-cyano-xcex2,xcex2-diphenylacrylic acid ethyl -ester or isooctyl ester, xcex1-carbomethoxy-cinnamic acid methyl ester, xcex1-cyano-xcex2-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, xcex1-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N-(xcex2-carbomethoxy-xcex2-cyanovinyl)-2-methyl-indoline, Sanduvor(copyright) PR25, dimethyl p-methoxybenzylidenemalonate (CAS #7443-25-6), and Sanduvor(copyright) PR31, di-(1,2,2,6,6-pentamethylpiperidin-4-yl) p-methoxybenzylidenemalonate (CAS #147783-69-5).
2.5. Nickel compounds, for example nickel complexes of 2,2xe2x80x2-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amine stabilizers, for example 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, 1,1xe2x80x2-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione, bis(1-octyloxy-2,2,6,6-etramethylpiperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-piperidyl) succinate, linear or cyclic condensates of N,Nxe2x80x2-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl )-1,3,5-triazine and 1,2-bis(3-amino-propylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl4-piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,Nxe2x80x2-bis-formyl-N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, diester of 4-methoxy-methylene-malonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, reaction product of maleic acid anhydride-xcex1-olefin-copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.
The sterically hindered amine may also be one of the compounds described in GB-A-2301106 as component I-a), I-b), I-c), I-d), I-e), I-f), I-g), I-h), I-i), I-j), I-k) or I-l), in particular the light stabilizer 1-a-1, 1-a-2, 1-b-1, 1-c-1, 1-c-2, 1-d-1, 1-d-2, 1-d-3, 1-e-1, 1-f-1, 1-g-1, 1-g-2 or 1-k-1 listed on pages 68 to 73 of said GB-A-2301106.
The sterically hindered amine may also be one of the compounds described in EP 782994, for example compounds as described in claim 10 or 38 or in Examples 1-12 or D-1 to D-5 therein.
2.7. Sterically hindered amines substituted on the N-atom by a hydroxy-substituted alkoxy group, for example compounds such as 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine, the reaction product of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine with a carbon radical from t-amylalcohol, 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) glutarate and 2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethyl-amino)-s-triazine.
2.8. Oxamides, for example 4,4xe2x80x2-dioctyloxyoxanilide, 2,2xe2x80x2-diethoxyoxanilide, 2,2xe2x80x2-dioctyloxy-5,5xe2x80x2-di-tert-butoxanilide, 2,2xe2x80x2-didodecyloxy-5,5xe2x80x2-di-tert-butoxanilide, 2-ethoxy-2xe2x80x2-ethyloxanilide, N,Nxe2x80x2-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2xe2x80x2-ethoxanilide and its mixture with 2-ethoxy-2xe2x80x2-ethyl-5,4xe2x80x2-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.9. Tris-aryl-o-hydroxyphenyl-s-triazines, for example known commercial tris-aryl-o-hydroxyphenyl-s-triazines and triazines as disclosed in, WO 96/28431, EP 434608, EP 941989, GB 2,317,893, U.S. Pat. Nos. 3,843,371; 4,619,956; 4,740,542; 5,096,489; 5,106,891; 5,298,067; 5,300,414; 5,354,794; 5,461,151; 5,476,937; 5,489,503; 5,543,518; 5,556,973; 5,597,854; 5,681,955; 5,726,309; 5,942,626; 5,959,008; 5,998,116 and 6,013,704, for example 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine, Cyasorb(copyright) 1164, Cytec Corp, 4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine, 2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine, 2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)-phenyl]-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxy-propyloxy)phenyl]-s-triazine, 2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-xcex1-cumylphenyl]-s-triazine (* denotes a mixture of octyloxy, nonyloxy and decyloxy groups), methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)-phenyl]-s-triazine}, methylene bridged dimer mixture bridged in the 3:5xe2x80x2, 5:5xe2x80x2 and 3:3xe2x80x2 positions in a 5:4:1 ratio, 2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-xcex1-cumylphenyl)-s-triazine, 2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine, 2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine, mixture of 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)-phenyl)-s-triazine and 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tridecyloxy-2-hydroxypropoxy)-phenyl)-s-triazine, Tinuvin(copyright) 400, Ciba Specialty Chemicals Corp., 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazine and 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine.
3. Metal deactivators, for example N,Nxe2x80x2-diphenyloxamide, N-salicylal-Nxe2x80x2-salicyloyl hydrazine, N,Nxe2x80x2-bis(salicyloyl) hydrazine, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,Nxe2x80x2-diacetyladipoyl dihydrazide, N,Nxe2x80x2-bis(salicyloyl)oxalyl dihydrazide, N,Nxe2x80x2-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4xe2x80x2-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxaphosphepin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g][1,3,2]dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2xe2x80x2,2xe2x80x3-nitrilo[triethyltris(3,3xe2x80x2,5,5xe2x80x2-tetra-tert-butyl-1,1xe2x80x2-biphenyl-2,2xe2x80x2-diyl)phosphite], 2-ethylhexyl(3,3xe2x80x2,5,5xe2x80x2-tetra-tert-butyl-1,1xe2x80x2-biphenyl-2,2xe2x80x2-diyl)phosphite.
Especially preferred are the following phosphites:
Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos(copyright) 168, Ciba Specialty Chemicals Corp.), tris(nonylphenyl) phosphite,
5. Hydroxylamines, for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxyl-amine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
6. Nitrones, for example N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
7. Amine oxides, for example amine oxide derivatives as disclosed in U.S. Pat. Nos. 5,844,029 and 5,880,191, didecyl methyl amine oxide, tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amine oxide.
8. Benzofuranones and indolinones, for example those disclosed in U.S. Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643; DE-A4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuran-2-one, 3,3xe2x80x2-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, Irganox(copyright) HP-136, Ciba Specialty Chemicals Corp., and 3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
9. Thiosynergists, for example dilauryl thiodipropionate or distearyl thiodipropionate.
10. Peroxide scavengers, for example esters of xcex2-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(xcex2-dodecylmercapto)propionate.
11. Polyamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
12. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
13. Nucleating agents, for example inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers).
14. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
15. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, dyes, optical brighteners, rheology additives, catalysts, flow-control agents, slip agents, crosslinking agents, crosslinking boosters, halogen scavengers, smoke inhibitors, flameproofing agents, antistatic agents, clarifiers such as substituted and unsubstituted bisbenzylidene sorbitols, benzoxazinone UV absorbers such as 2,2xe2x80x2-p-phenylene-bis(3,1-benzoxazin-4-one), Cyasorb(copyright) 3638 (CAS #18600-59-4), and blowing agents.
16. Other biocides, for example fungicides such as 3,5-dimethyl-tetrahydro-1,3,5-2H-thiodiazin-2-thione, Bis-tributyltinoxide, 4.5-dichlor-2-n-octyl-4-isothiazolin-3-one, N-butyl-benzisothiazoline, 10,10xe2x80x2-oxybisphenoxyarsine, zinc-2-pyridinthiol-1-oxide, etc., and algicides such as 2-methylthio-4-cyclopropylamino-6-(xcex1,xcex2-dimethylpropylamino)-s-triazine, 2-methylthio-4-cyclopropylamino-6-tert-butylamino-s-triazine, 2-methylthio-4-ethylamino-6-(xcex1,xcex2-dimethylpropylamino)-s-triazine, etc.
In general the plastic resins with antimicrobial activity according to the present invention may be selected from:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE) and medium density polyethylene (MDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
a) radical polymerization (normally under high pressure and at elevated temperature).
b) catalytic polymerization using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either p- or s-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbomene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(xcex1-methylstyrene).
6. Copolymers of styrene or xcex1-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/unsaturated ester, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylenelbutylene/styrene or styrene/ethylene/propylene/styrene.
7. Graft copolymers of styrene or xcex1-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, SAN, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from xcex1,xcex2-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS. Polyesters and polyester copolymers as defined in U.S. Pat. No. 5,807,932 (column 2, line 53), incorporated herein by reference.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from polyepoxides, for example from bis glycidyl ethers or from cycloaliphatic diepoxides.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example-cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/-EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPOIPA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.
29. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
31. Polysiloxanes such as the soft, hydrophilic polysiloxanes described, for example, in U.S. Pat. No. 4,259,467; and the hard polyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.
32. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins. The unsaturated acrylic resins include the urethane acrylates, polyether acrylates, vinyl or acryl copolymers with pendant unsaturated groups and the acrylated melamines. The polyketimines are prepared from polyamines and ketones in the presence of an acid catalyst.
33. Radiation curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer.
34. Epoxymelamine resins such as light-stable epoxy resins crosslinked by an epoxy functional coetherified high solids melamine resin such as LSE-4103 (Monsanto).
Preferably, the plastic resin is selected from the group consisting of LDPE, HDPE, MDPE, PP, ABS, SAN, PS, PMMA, PET, polyamide, PVC, polymer latex, PUR, TPU, UF and UP.
The mixture of components a) and b) is preferably present in the antimicrobial plastic film, fiber or article in an amount of about 0.005 to about 10% by weight, relative to the plastic material. An amount of from about 0.01 to about 5% by weight or about 0.05 to about 3% by weight of the mixture of components a) and b) relative to the plastic material is especially preferred.
The mixture of components a) and b) and optional further additives may be added to the plastic resin, e.g. the polyolefin, individually or mixed with one another. If desired, the individual components of an additive mixture can be mixed with one another in the melt (melt blending) before incorporation into the plastic material.
The incorporation of the mixture of components a) and b) and optional further additives into the plastic material is carried out by known methods such as dry mixing in the form of a powder, or wet mixing in the form of solutions or suspensions. Components a) and b) and optional further additives may be incorporated, for example, before or after molding or also by applying the dissolved or dispersed stabilizer mixture to the plastic material, with or without subsequent evaporation of the solvent. The mixture of components a) and b) and optional further additives can also be added to the plastic material in the form of a masterbatch which contains these components in a concentration of, for example, about 2.5% to about 70% by weight; in such operations, the polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latices.
If added to a plastic resin in the form of a masterbatch or concentrate, the novel antimicrobial mixture of components a) and b) is added via carriers such as LDPE, HDPE, MDPE, PP, ABS, SAN, PS, acrylates, PMMA, polyamide, polyesters, PVC, polymer latex, styrene, polyol, TPU, unsaturated esters, urea, paraformaldehyde, water emulsion, etc. The total concentration of a)+b) in the carriers is from about 2.5% to about 70% by weight based on the weight of the carrier.
Components a) and b) and optional further additives can also be added before, during or after polymerization or crosslinking.
Components a) and b) and optional further additives can be incorporated into the plastic material in pure form or encapsulated in waxes, oils or polymers.
Components a) and b) and optional further additives can also be sprayed onto the plastic material. They are able to dilute other additives (for example the conventional additives indicated above) or monomers or their melts so that they can be sprayed also together with these additives onto the plastic material. Addition by spraying during the deactivation of the polymerization catalysts is particularly advantageous, it being possible to carry out spraying using, for example, the steam used for deactivation.
In the case of spherically polymerized polyolefins it may, for example, be advantageous to apply components a) and b) and optionally together with other additives, by spraying.
The following examples illustrate the invention in more detail. They are not to be construed as limiting the instant invention in any manner whatsoever. The invention is declared to cover all changes and modifications of the specific examples which do not constitute departure from the spirit and scope of the invention. Parts and percentages are by weight.

Mixtures of phenolic and inorganic materials with antimicrobial activity


Actuating equipment for a gate valve or penstock uses both compressed air and hydraulic oil to obtain the advantages of both. A control valve directs air to a hydraulic reservoir so as to drive oil at the air pressure into one chamber of a double acting cylinder and piston connected to the gate. When the gate is not being moved it is locked in position by an air operated valve preventing oil flow. A normally energized solenoid operated control valve opens when electrical power fails so as to direct stored air from a reservoir to move the gate to a fail-safe position.. Air pipelines may provide communication over some distance from the control valves to the gate valve or penstock. This can avoid running electric cable through a hazardous environment, while to give fail-safe operation in the event of damage to the pipelines, these are placed within a larger bore line supplying air to hold closed an air operated valve, which, in the event of loss of pressure in this line opens so that stored air moves the gate to its fail-safe position and also operates a valve preventing movement away from that position.. Means are provided to apply an enhanced force to the gate for part of its travel.

1. Field of the Invention
The invention relates to actuating equipment for valves having a reciprocally moveable gate for blocking the flow path, such as gate valves, penstocks and the like.
2. Description of the Prior Art
Gate valves and penstocks have customarily been fitted with handwheels to turn screwed rods connected to the valve gate. Devices to render operation faster and/or less laborious, or to provide for remote operation are known, for example hydraulic actuators are disclosed in U.S. Pat. Nos. 3,226,078, 3,111,298 and 3,086,745.
Fluid driven devices are well suited to the operation of gate valves and penstocks since they generate reciprocating motion directly by means of a piston and cylinder. However, known devices utilise only a single fluid, either compressed gas or hydraulic oil and both fluids have disadvantages. Compressed gas piston and cylinders generally operate with an uncontrolled rapidity and are inherently unsuited to moving the gate of a valve or penstock over less than its full travel. Because of its resilience compressed gas would not hold a gate firmly.
Equipment handling hydraulic oil tends to be dirty and is messy to maintain--especially where dismantling is required--leading to greater maintenance costs and longer maintenance downtimes. Remote operation requires electrical equipment and runs of electric cable which may need to be protected from its environment or which may itself represent a hazard.
Electro-mechanical actuators remain in use, presumably because of the above mentioned or other disadvantages of fluid driven devices. One device which has been introduced (in the United Kingdom at least) provides an indication of the level of elaboration and complexity which is at present regarded as acceptable. This device has an electric motor to turn the screwed rod of the valve or penstock, but the motor is not fixedly mounted. Instead it is part of an assembly carried on the screwed rod. Movement of the assembly is opposed by springs which are sufficient to restrain it against the motor torque only as long as the gate of the valve or penstock continues to move. When the gate reaches the end of its travel the motor assembly moves on the screwed rod, and its motion is detected by limit switches which turn off the motor. Should a limit switch fail to function the motor assembly would screw itself off the screwed rod, or stall when it reaches an obstruction to its further movement with concomitant overloading of the motor.
Subsequent to making the present invention the applicant has become aware of proposals for equipment which supplies compressed gas to an oil reservoir to pressurize hydraulic oil to the pressure of the gas. None of these proposals, however, has anything to do with the actuation of gate valves or penstocks; they occur in other arts. U.K. Specification Nos. 1,202,913 and 1,321,291 relate to landing gear for vehicle semitrailers; U.K. Specification No. 1,392,418 is concerned with apparatus for moving an X-ray generator; U.S. Pat. Nos. 2,573,993 and 2,403,912 relate to hydraulic presses, in the latter specification there is disclosure of using compressed air to raise oil to the air pressure to move the press and subsequently to an enhanced pressure to complete the press stroke, and U.S. Pat. No. 3,370,824 describes a ladle for molten metal which carries a supply of compressed gas to drive a hydraulic oil pump for actuating a stopper rod constituting a valve for the molten metal.


A computerized method and apparatus for evaluating content on a computer network. The method includes obtaining a quality score of content configured for display with a web page, wherein the quality score is based at least in part on keywords associated with the content and either a search query or metadata associated with the web page. The method also includes identifying a user metric of a computing device associated with the search query or the metadata. The method further includes generating an adjusted quality score of the content based on the quality score and the user metric. The method also includes selecting a parameter for an auction based on the adjusted quality score, wherein the parameter indicates a relation between a bid value based auction and a content quality based auction.

The present disclosure relates generally to online advertisements. In particular, the present disclosure relates to determining which candidate advertisements to show to an online user, based in part on the user's browsing history.
One way online companies make money is by either offering items for purchase as online content such as online advertisements, or by offering a portion of their web site to content and receiving a monetary renumeration whenever an online users clicks on content impressed on their web site (called cost-per-click).

This patent is subject to a terminal disclaimer.

Content evaluation based on users browsing history


Aqueous release coating compositions for application to substrates having low absorption thereinto, excellent adhesion thereto, and easy and quick release and removal therefrom comprising:. from about 3% to about 8% of polyvinyl alcohol; PA1 from about 9% to about 35% clay; PA1 from about 5% to about 12% of an adhesive binder; and PA1 from about 49% to about 75% of water.. All percentages being by weight, based on the total weight of the aqueous release coating composition.. The resulting release-coated substrates are also included in the inventive concept.

Aqueous release coating compositions have been used for many years for application to various substrates, whereby various materials may be placed in adhering contact with such release-coated substrates but wherein such various materials may be easily and quickly released and removed from such release-coated substrates at a subsequent time.
Release coating compositions commonly in present commercial and industrial use contain conventional release agents, such as a silicone polymer, or a stearate chromium complex, or other relatively expensive materials, or other relatively less expensive release agents, such as polyvinyl alcohol.
However, even polyvinyl alcohol is relatively expensive, as compared to other commercial materials and, particularly in those applications where the polyvinyl alcohol is applied to a more or less porous substrate and is undesirably absorbed thereinto, it is desired that either the concentration of the polyvinyl alcohol in the release coating composition be reduced to an absolute minimum, or that measures be taken to reduce the undesirable absorption of the polyvinyl alcohol into the more or less porous substrate.
Of course, the substrate could be initially pre-treated with a primer coating or sealing compound, such as a thin layer of a relatively hard wax, or similar material, which would materially prevent the polyvinyl alcohol from undesirably soaking into the substrate, but such practice does not markedly reduce the materials-cost factor involved and actually in many instances increases the overall production-cost factor by the introduction of an additional processing step in the overall manufacturing cycle.

Aqueous release coating compositions and substrates coated therewith


A method of making an adsorbent which includes: a) thermally drying dewatered sewage sludge to form granulated organic fertilizer; b) treating the fertilizer with mineral oil; and c) pyrolyzing the treated fertilizer at temperatures between about 600° C. and about 1000° C. The disclosure is also directed to adsorbents made by this method and to the processes of removing acidic gas or gases from wet gas streams by putting an adsorbent in contact with the wet gas stream and allowing the adsorbent to adsorb the acidic gas or gases.

All references cited and discussed below in this specification are incorporated herein by reference in their entirety and to the same extent as if each reference was individually incorporated by reference. In the case of conflicting terminology, the present disclosure shall control.
Growing concerns about the environment have resulted in the development of new environmentally friendly technologies, new materials, and new ways to reduce and minimize wastes. One of the wastes produced by contemporary society in abundant quantity is municipal sewage sludge, euphemistically often referred to as biosolids. Biosolids are a mixture of exhausted biomass generated in the aerobic and anaerobic digestion of the organic constituents of municipal sewage along with inorganic materials such as sand and metal oxides.
Various methods have been proposed for the disposal of municipal sewage sludge, including ocean dumping, landfilling, cropland application and incineration. Other methods that have been used to dispose of or utilize municipal sewage sludge include road surfacing, conversion to fertilizer, compression into building blocks, and carbonization.
The application of raw sewage sludge as a fertilizer produces odor problems and is also associated with the risk of contamination of the soil by heavy metals and pathogens. A more efficaceous and safer alternative is the pyrolytic carbonization of sludge to obtain useful sorbents.
Carbonization of sludge in the presence of chemical activating agents, such as zinc chloride and sulfuric acid produces sorbents, having applications in processes such as removal of organics and chlorinated organics in the final stages of water cleaning.
The process of carbonization of biosolids has been studied in detail using different chemical agents and various conditions. In general, materials obtained as a result of the treatment have surface areas between 100 and 500 m2/g, but their performance as adsorbents has been demonstrated to be much worse than that of activated carbons.
Since hydrogen sulfide (H2S) is the main source of odor from waste water treatment plants, the possibility of using sewage sludge as a source of adsorbents for H2S is appealing. Because sewage sludge contains a considerable amount of organic nitrogen, carbonization of such species can lead to the creation of basic nitrogen groups within the carbon matrix which have been proven to be important in the oxidation of H2S. Another advantage to the use of sludge as a starting material is the presence of significant amounts of iron that is added to the raw sludge as a dewatering conditioner. This is considered to be a catalyst for H2S oxidation.
Primarily, caustic-impregnated carbons have been used as adsorbents of hydrogen sulfide at waste water treatment plants. Because of the presence of caustic compounds, such as KOH or NaOH, their pH is high, and hydrogen sulfide is oxidized to elemental sulfur. The process is fast and caustic-impregnated carbons have high hydrogen sulfide breakthrough capacity, around 140 mg/g, measured using accelerated test.
Caustic-impregnated carbons, although efficient for H2S removal, have many disadvantages. The disadvantages of caustic-impregnated carbons include the following:    1) limited capacity for physical adsorption of volatile organic compounds (VOCs) due to the presence of caustic materials in the carbon pore system;    2) low self-ignition temperature which may result in fire inside the carbon vessel;    3) special safety precautions in dealing with caustic materials have to be applied;    4) high density because of the presence of water; and    5) higher cost than that of unmodified carbons.
Thus, there is a great interest in the development of new types of adsorbents for use in waste water treatment facilities.
The following patents and publications provide relevant background to the present invention:
U.S. Pat. Nos. 3,619,420, 3,998,756, 3,887,461, 4,122,036, and 5,356,849; Adib et al., J. Colloid Interface Sci., 1999, 214, 407–415; Cariaso et al., Carbon, 1975, 13: 233–239; Chiang et al., Can. J. Chem. Eng., 1987, 65: 922–927; Katoh et al., Appl. Cat. B: Environ., 1995, 6: 255–262; Lu et al., Fuel, 1995, 74: 344–348; Lu et al., Gas Sep Purif., 1996, 10: 103–111; Lu et al. Environ Tech., 1995, 16, 495; Piskorz et al., Ind. Proc. Des. Dev., 1996, 25: 265–270; and Stejns et al., Ind. Eng. Chem. Prod. Res. Dev., 1977; 16: 35–41.

Preparation of adsorbents from organic fertilizer and mineral oil and their application for removal of acidic gases from sulfur containing wet gas streams

Research Foundation of The City University of New York


The present invention relates to a water soluble acidic copper wood preservative composition with good copper fixation, and without environmental challenged hexavalent chromium. The composition comprises a water soluble acidic copper pesticide combined with aluminum nitrate wherein the weight ratio of aluminum nitrate to copper ranges from 1 to 10 to 10 to 1.

Not Applicable
Not Applicable
Not Applicable
The field of endeavor to which this invention pertains relates to the preservation of wood with water soluble acidic copper pesticides, and to compositions containing acidic copper and aluminum nitrate in weight ratios ranging from 1 to 10 to 10 to 1. Problems in the prior art with acidic copper wood preservation include difficulty in achieving copper fixation. Fixation has been historically achieved by combining chromates with the acidic copper. Now, there is increasing environmental pressure against the use of chromates, and this solution to copper fixation is no longer viable.
Acidic copper wood preservatives include both inorganic and organic salt of the metal. These are usually prepared by reacting an acid with copper metal, copper oxide, copper carbonate, or copper hydroxide. Copper salts of the stronger acids are more water soluble, and more difficult to fix in the wood. Aluminum nitrate is a well known chemical; but it has not been used in commercial wood preservation.
The claimed invention relates to an acidic copper wood preservative composition with good copper fixation, and without chromates. My composition comprises a water soluble acidic copper pesticide combined with aluminum nitrate wherein the weight ratio of aluminum nitrate to copper ranges from 1 to 10 to 10 to 1. The existing problem solved by my invention consists of the elimination of environmental problems associated with the use of hexavalent chromium.
The preferred embodiment of my invention uses copper dissolved with propionic acid, and combined with aluminum nitrate. The preferred copper source is copper hydroxide, and the preferred aluminum nitrate is the technical 60% material in water. The exact amount of propionic acid needed to dissolve the copper depends upon the amount of aluminum nitrate used, and its excess nitric acid . Hence, it is preferred propionic acid be added to the copper and aluminum nitrate mix until the copper just dissolves. The preferred weight ratio of aluminum nitrate to copper is near 1 to 1; but may vary widely. Example 1 illustrates the preparation of the preferred embodiment of my composition invention wherein the ingredients were added in the order listed with vigorous mixing. It will be obvious to those skilled in the art that concentrate wood preservatives can be produced in similar manner.

Acidic copperxe2x80x94aluminum nitrate wood preservative


Various methods are provided for tracking eye movement and estimating point of regard. Methods may include: providing for capture of a first image of a first eye of a person; providing for capture of a first image of a second eye of the person; and providing for capture of a first image of a field of view of the person. The method may include estimating a first iris and pupil boundary for the first eye using the first image of the first eye; estimating a second iris and pupil boundary for the second eye using the first image of the second eye; determining a first foveated retinal image related to the first eye based on the first image of the first eye and the first iris and pupil boundary of the first eye; and determining a second foveated retinal image related to the second eye based on the first image of the first eye and the second iris and pupil boundary for the second eye.

Tracking eye movement and the object of interest that a person may be viewing is an important feature for many applications in modern computing. Eye movement can be used to determine, for example, if a person is distracted or focused on driving a vehicle, which may be instrumental in crash avoidance systems used in the automotive field. Further, eye tracking and gaze can be used to determine the level of interest of a person in response to advertising, entertainment, or other visual displays. This information may be useful to advertisers, entertainment producers, etc., to determine what attracts the most visual attention from viewers, thereby enabling the advertisers or entertainment producers to develop more focused advertising or entertainment. Various other uses for eye tracking and tracking eye gaze may be used in various fields for a wide variety of purposes. However, improvements to the accuracy of tracking eye gaze and eye movement are desirable to ensure more effective use of eye tracking data.

Method, apparatus, and computer program product for tracking eye gaze and eye movement


Aromatic mono-, di-, or trihydroxy compounds are used alone or containing peel strength-improving additives, in association with a polyurethane adhesive, for adhering a polyurethane-coated nylon fabric to another polyurethane-coated nylon fabric to form a polyurethane-coated nylon composite, and for adhering a nylon fabric coated with an aluminum flake-containing polyurethane to a polyurethane-coated nylon fabric. Additionally, aromatic mono-, di-, or trihydroxy compounds are utilized in association with a polyurethane adhesive for forming a lamina composition comprising a polyurethane film adhered to a nylon fabric.

The use of aromatic hydroxy compounds for improved adhesion between nylon materials is known, but the use of aromatic hydroxy compounds alone or containing peel strength-improving additives, to improve adhesion between polyurethane coated nylon fabrics or between polyurethane and nylon, is not known. Heretofore, various polyamide band membranes have been bonded. For example, Romanian Patent 71486 of Oct. 21, 1977, discloses adhesives containing 20 to 60 percent di- or trihydric phenols, 0.1 to 10 percent coumarone-indene resin or phenol formaldehyde resin. Polyamide bands were bonded with a composition containing resorcinol, 30 percent coumarone-indene resin 5, etc.
In Russian Patent 834,071 of May 30, 1981, disclosed is a method for adhering shoe soles and uppers by treating the soles with a composition containing low molecular weight nylon 6, formic acid, resorcinol, and alcohol. An adhesive-containing low temperature neoprene rubber is prepared by a sulfur control polymerization containing phenol-formaldehyde resin. The adhesive is applied to both soles and uppers, dried, activated by heat treatment, and bonded by hot pressing the two adhesive-coated surfaces together.

Composition for adhesion of polyurethane-coated nylon fabrics


The present invention implements efficient transmission of captured images while also maintaining high-resolution image quality. The present invention is an image processing method for an X-ray image diagnosis apparatus, the method including the steps of: obtaining the effective bandwidth for transmitting captured images; obtaining imaging conditions; calculating the respective resulting data amounts when a captured image captured under the conditions is compressed using lossless and lossy compression, mixing the captured images compressed losslessly and lossily, and determining the mix ratio so that the transmission amount per unit of time when multiple captured images are transmitted is less than the effective bandwidth; and transmitting the multiple captured images compressed losslessly and lossily at the determined ratio.

1. Field of the Invention
The present invention relates to an image processing technique for processing images captured by an X-ray image diagnostic apparatus.
2. Description of the Related Art
Imaging systems using photomultipliers as X-ray detection units have hitherto been widely utilized as X-ray image diagnostic apparatuses for making medical diagnoses. Such imaging systems, in which a captured image that has undergone phototransformation in such a photomultiplier is processed in analog form and displayed in a monitor, are called "analog image intensifiers".
However, X-ray image diagnostic apparatuses utilizing digital X-ray imaging systems that digitally detect X-rays and form captured images (called "digital X-ray image diagnostic apparatuses" hereinafter) are becoming more common as of late, taking the place of such analog image intensifiers.
An apparatus that uses a flat panel detector (abbreviated as "FPD" hereinafter) as its detection device can be given as a representative example of a digital X-ray image diagnostic apparatus.
FPDs are provided with units configured of, for example, solid-state image sensors having high X-ray sensitivity that convert detected X-rays into electrical signals based on their intensity, and output the electrical signals. Alternatively, the FPDs are provided with units that combine a scintillator, which absorbs the energy of the X-rays and emits fluorescent light of an intensity in accordance therewith, with a photoelectric conversion element, which has a high sensitivity to visible light and converts that light into electrical signals based on the intensity thereof. The FPDs are provided with such units as well as A/D converters that digitize the analog signals from those units.
Digital X-ray image diagnostic apparatuses that use such FPDs are capable of realizing wider dynamic ranges and obtaining higher-resolution images than X-ray image diagnostic apparatuses that use conventional analog image intensifiers. Recently, digital X-ray image diagnostic apparatuses are also showing properties that are not inferior to conventional image intensifiers in terms of frame rates when capturing moving pictures.
Furthermore, because digital X-ray image diagnostic apparatuses enable the captured images to be handled in digital form, they allow more advanced image processing to be performed, without drops in image quality during processing, transmission, and storage.
The spread of digital X-ray image diagnostic apparatuses can therefore contribute to improvements in the accuracy of diagnoses due to the higher image quality. Such apparatuses can also contribute to the implementation of new types of medical systems, such as data management facilitated by the digital nature of the images, links with other medical devices through digital networking, and so on.
Recently, remote medical services are garnering attention as one such new medical system.
In the past, it has been difficult to perform emergency medical procedures, perform examinations and treat problems using advanced devices, and so on in regions that are unable to obtain specialized medical care, such as remote islands that lack general hospitals. Therefore, when emergency medical care is necessary in such regions, doctors working outside of their specialization generally provide the initial care, after which the patient is transported to a general hospital capable of more advanced medical care. However, it often takes time to select the hospital to transport the patient to, and to actually transport the patient to that hospital.
In light of this, if a communication path capable of transferring data between clinics on remote island and general hospitals in larger cities could be laid and remote medical services provided, captured images obtained using an X-ray image diagnostic apparatus on the island could be viewed by specialists in a general hospital.
Implementing remote medical services using such an X-ray image diagnosis system makes it possible to obtain high-level examination/treatment services under the instruction of a specialist even in regions that lack advanced medical facilities.
It goes without saying that when implementing such a remote medical service, it is necessary for the transmitted captured images to be of a quality sufficient for diagnosis and treatment, and it is particularly necessary, in terms of diagnostic performance, for the image resolution to be sufficiently high. At the same time, it is particularly necessary, when making diagnoses and performing treatment using moving pictures, to ensure a frame rate sufficient for making diagnostic and treatment instructions.
However, there are often constraints on the transmission bandwidth that can actually be used, and in light of this, it is necessary to efficiently encode captured images in order to reduce the data amount thereof before transmitting the images. However, because the captured images are used for diagnoses and treatment, excessive compression coding leading to a drop in image quality is unacceptable.
Therefore, when implementing such a remote medical service, it is important to efficiently transmit captured images of the required quality within the effective bandwidth for transmission (in other words, to implement efficient transmission while also maintaining high-resolution image quality).
Selectively changing the method used to encode the captured images is useful as a way to implement efficient transmission while also maintaining high-resolution image quality in such a manner. Japanese Patent Laid-Open Nos. 06-209926 and 01-189772 (hereinafter referred to as Patent Documents 1 and 2 respectively) are known as techniques for selectively changing the method used to encode captured images.
Patent Document 1 discloses a configuration that changes the amount of data obtained (frame rate, X-ray amount) and the compression coding method depending on whether a region is a specified region of interest or not. Patent Document 2, meanwhile, discloses a configuration that detects biological changes and changes the compression coding method based on the detected changes. In Patent Document 2, frames considered more important in terms of biological changes are encoded using a lossless compression method, whereas other frames are encoded efficiently using a lossy compression method.
However, the configurations disclosed in Patent Documents 1 and 2 are not intended to implement remote medical services, and do not aim to control encoding captured images within the effective bandwidth for transmission. Therefore, applying such configurations as-is to a remote medical service may result in the data amount exceeding the effective bandwidth for transmission.
To be more specific, with Patent Document 1, the effects of the compression coding are reliable when parts necessary for diagnosis and parts unnecessary for diagnosis coexist within the same frame. However, this technique is ineffective when, for example, irradiating only an area of interest with X-rays and not imaging the other areas in order to reduce the amount of X-ray irradiation as much as possible, as with radioscopy imaging.
Meanwhile, Patent Document 2 changes the compression coding method based on time, as opposed to Patent Document 1, which changes the compression coding method based on space; thus a certain degree of effectiveness can be expected. However, because the data amount depends on biological changes, there is no guarantee that that data amount will fall within the effective bandwidth for transmission.

X-ray image diagnostic apparatus and control method, and image processing method


The quality of staining histological specimens has an impact on the histological assessment of the specimen. One of the causes for variability in the accuracy is the variations in the staining of the specimens to be tested in the working laboratories. The present invention provides a method for assessing the staining quality in a working laboratory and providing a quantitative quality measure for the staining quality. Thereby, it is possible for each working laboratory to evaluate their staining quality and to get feedback of how to improve the quality. The invention further relates to a system and a software program for carrying out the method.

When performing histological assessments of specimens containing cells it is relevant to consider the quality of the staining before considering the histological findings in the specimen. Too little or too much staining as compared to a protocol may lead to incorrect evaluations of the specimen. In particularly if the specimen relates to tumor cells it may be crucial for the patient that the laboratory is capable of staining and evaluating the specimens correctly.
The human epidermal growth factor, commonly referred to as HER2, is amplified in approximately 18% to 20% of breast cancers. HER2 overexpression is associated with clinical outcomes in patients with breast cancer. Several studies have shown that agents that target HER2 are remarkably effective in both the metastatic and adjuvant settings. Trastuzumab (Herceptin; Genentech, South San Francisco, Calif.), a humanized monoclonal antibody, improves response rates, time to progression, and even survival when used alone or added to chemotherapy in metastatic breast cancer. Trastuzumab is also active as a single agent and was approved in 1998 by the US Food and Drug Administration for the treatment of metastatic disease.
The ASCO/CAP panel have issued guideline recommendations for HER2 testing in breast cancer, and it is recommended that HER2 status should be determined for all invasive (early stage or recurrence) breast cancer on the basis of one or more Her2 test results [1]. These guideline recommendations are adopted to a varying degree by different local national boards across the world.
In daily practice between 80 and 90 percent of primary HER2 testing in fx the United States is done with immunohistochemistry (IHC), while only 10 to 20 percent is done with FISH. Approximately 10 to 20 percent of IHC test results fall into the so-called "indeterminate" range, and those specimens are re-tested using FISH which is widely considered the Gold Standard. One reason for this practice is also price, where an IHC assay may cost $100 to $150, and a FISH assay may be double or triple that price
The ASCO/CAP guidelines were recently updated in November 2013 [2]. The Update Committee was concerned about false-negative and false-positive HER2 assessments. For example, a false-negative test result could lead to denial of trastuzumab treatment for a patient who could benefit from it. False-positive results could lead to the administration of potentially toxic, costly, and ineffective adjuvant HER2-targeted therapy for 1 year.
The purpose of the ASCO/CAP guidelines is to improve the accuracy of human epidermal growth factor receptor 2 (HER2) testing in invasive breast cancer and its utility as a predictive marker.
Despite efforts to provide detailed guidelines for improving the accuracy of the testing of HER2 protein expression, numerous reports of variability in interpretation have raised uncertainty about the reliability of results.


An apparatus for transferring electrical current to or from a moving electrically conductive wire includes a rod-shaped electrically conductive member at an angle with a normal straight line of wire travel. The conductive member is received within a bore of a support body. A sleeve is located within the support body bore and between the rod-shaped conductive member and the bore wall. The sleeve includes a channel which is coplanar with the normal straight line of wire travel and communicating with the conductive member outer surface. The channel forms a wire passageway. The moving wire travels through the wire passageway and in contact with the conductive member circular outer surface. The conductive member is rotated about its longitudinal axis for exposing multiple surfaces to the wire and the sleeve is fixed to the support body to prevent movement thereof during such rotation of the conductive member. The sleeve can be made of a non-conductive material.

The placing of electrical current on a moving wire is currently required and is being done in at least the electrical discharge machine (EDM) industries and welding industries. This is currently normally accomplished by providing various shaped current pickups which are electrically charged. The moving wire slides or rubs against the electrically charged surface of the current pickup thus transferring electrical current therethrough to and from the moving wire. One common pickup is generally cylindrically shaped with a bore therethrough. The wire is received through the pickup bore and, because the current pickup bore is offset from the straight line of wire travel, the moving wire electrode rubs against the interior surface of the bore making the necessary electrical contact for transferring current to the moving wire. Other current pickup devices are made with various shaped contact surfaces and are pushed toward the taut moving wire electrode or placed in the normal straight line of wire travel causing the wire to rub against the current pickup contact surface thereby making the necessary electrical contact. Current pickups such as those described hereinabove are, for example, disclosed in U.S. Pat. No. 4,896,013 and U.S. Pat. No. 4,539,459.
However, the current pickups which are presently known and used have substantial shortcomings and drawbacks. Like all current pickups, as the moving wire slides against the pickup contact surface, the current pickup tends to wear and the wire causes a groove to be formed in the pickup through the original contact surface. Once the groove becomes sufficiently large in depth, the wire tends to bind therein causing wire breakage and requiring the stopping of, for example, the EDM operation and rethreading of the wire. As the groove is formed, the wire also tends to get closer to the normal straight line of wire travel (straighter) and even though the wire remains taut, there is insufficient contact between the wire and the new contact surface at the bottom of the groove for efficient current transfer. In view of this, after a particular contact surface has worn by a predetermined amount, the current pickup position is changed so as to provide a new contact surface or the entire current pickup itself is replaced.
Prior current pickups, however, provide relatively few contact surface positions whereat a new contact surface can be exposed to the moving wire. Typically, the cylinder-shaped pickups have a bore diameter only slightly larger than the wire diameter and, therefore, the maximum number of contact surfaces is four. Each of the contact surfaces for these current pickups are located on the current pickup bore surface at 90 degrees from each other with respect to the bore longitudinal axis. After these four contact surfaces have been exposed and worn, the current pickup is no longer useful and is replaced. Exposing the four different contact surfaces of the cylinder-type pickups, however, normally requires the disassembly of the various guide arm assembly components so as to gain access to the current pickup located therein and so that a tool or other means can be used for turning the current pickup about its longitudinal axis and exposing the new contact surface. An example of this is disclosed in U.S. Pat. No. 5,089,680. As can be appreciated, although this is generally acceptable, the disassembly of the entire guide arm to gain access to the current pickup can be cumbersome, time-consuming and, thus, costly. In addition, although other devices such as those disclosed in U.S. Pat. No. 4,994,643 have been devised for tilting and/or turning the cylindrical-type current pickup without disassembly of the entire guide arm, such devices of the past are somewhat complex and costly. Furthermore, even with such devices, the replacement of the current pickup, once all bore contact surfaces have been diminished still requires complete disassembly of the guide arm for gaining access to the current pickup and replacing the same. Again, this is somewhat cumbersome, time-consuming and costly.
Accordingly, a need exists for a current pickup apparatus that conveys electrical current to and from a moving wire and which overcomes the above-discussed disadvantages associated with prior current pickup assemblies and which further provides a substantial number of different contact surfaces on the pickup and which allows easy removing and replacing the pickup without disassembly of the guide arm assembly housing the pickup. In addition, a need exists for such apparatus which is both reliable and generally inexpensive to manufacture, assemble and operate.

Sleeve forming wire passageway around pickup


The present invention provides a method for evaluating the transparency and/or water holding capacity of a stratum corneum by using oxidized protein in the stratum corneum as an indicator.

Accurate determination of skin type (or skin status) is important in terms of providing effective skin care for maintaining healthy skin. Consequently, when providing skin care using cosmetics, for example, the skin type of a cosmetic user is evaluated through the asking of questions and so forth by a beauty technician. In addition, skin status or function is evaluated according to observed or measured parameters using various types of measuring instruments for the purpose of objectively evaluating skin type.
Research has recently been actively conducted on stratum corneum oxidized proteins in the relationship between aging accompanying aging of the skin and photoaging. Oxidized proteins consist mainly of proteins into which carbonyl groups have been introduced as a result of being subjected to oxidation, and in general, consist of those formed as a result of the NH2 groups of amino acid residues such as Lys, Arg and Pro in proteins being oxidized directly resulting in their conversion to carbonyl groups, and those formed as a result of lipid being oxidized to lipid peroxides, which in turn are degraded into highly reactive aldehydes that bind with protein. As a result of extensive research relating to aging, oxidized proteins are recognized to increase with aging (brain, liver, fibroblasts), in Alzheimer's disease, in progeria (Werner's syndrome), and the like.
In the skin, sebaceous lipid on the skin surface is oxidized by free radicals resulting in the formation of lipid peroxides. The formation of lipid peroxides initializes the oxidation of proteins, and once these lipid peroxides are formed, oxidation proceeds continuously, not only causing irritation on the skin surface, but also penetrating deep into the stratum corneum and damaging cells. Thus, by evaluating the properties of oxidized proteins of the skin, such as the amount present and their distribution state, and determining the skin type or skin status, those evaluation results can be expected to be used in some embodiments for determining the direction of subsequent skin care and selecting cosmetics. At present, however, although there is predicted to be some kind of vague relationship between oxidized proteins and skin damage, the manner in which the oxidation of stratum corneum protein actually affects the properties of the skin has yet to be determined.

Method for determining the degree of protein oxidation in a skin sample using oxidized protein in stratum corneum as an indicator


A flame-retardant aconitic acid-derived cross-linker, a process for forming a flame-retardant resin, and an article of manufacture comprising a material that contains a flame-retardant aconitic acid-derived cross-linker are disclosed. The flame-retardant aconitic acid-derived cross-linker can have at least two phosphoryl or phosphonyl moieties with allyl functional groups, epoxy functional groups, propylene carbonate functional group, or functionalized thioether substituents. The process for forming the flame-retardant polymer can include forming an aconitic acid derivative, forming a phosphorus-based flame-retardant molecule, and reacting the aconitic acid derivative with the phosphorus-based flame-retardant molecule to form a flame-retardant aconitic acid-derived cross-linker, and binding the cross-linker to a polymer. The aconitic acid derivative can be synthesized from aconitic acid obtained from a bio-based source. Examples of aconitic acid derivatives include carboxysuccinic acid, 2-(hydroxymethyl)-1,4-butenediol, and 2-(hydroxymethyl)-1,4-butanediol. The article of manufacture can further comprise an electronic component.

The present disclosure relates to bio-renewable flame-retardant compounds and, more specifically, flame-retardant cross-linkers derived from aconitic acid.
Bio-based, sustainable compounds can be used in the syntheses of substances that previously required petroleum-based raw materials. Examples of uses for bio-based compounds include polymers, flame retardants, cross-linkers, etc. There are numerous strategies for efficiently and inexpensively producing bio-based compounds on an industrial scale. Examples of these strategies can be found in fermentation technologies, membrane technologies, and genetic engineering. Aconitic acid (propene-1,2,3-tricarboxylic acid) is one example of a bio-based compound that can have applications as a component of various polymers, resins, and small molecules. Aconitic acid is an intermediate in the citric acid cycle, wherein it is acted upon by the aconitase enzyme. Bio-based materials, such as sugarcane or citric acid, are common sources of aconitic acid.

Flame-retardant aconitic acid-derived cross-linkers

International Business Machines Corporation