text:
|Publication number
|Publication type
|Application number
|Publication date
|May 31, 1988
|Filing date
|Feb 18, 1987
|Priority date
|Apr 2, 1984
|Fee status
|Also published as
|Publication number
|John C. Chang
|Original Assignee
|Minnesota Mining And Manufacturing Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (23), Non-Patent Citations (2), Referenced by (21), Classifications (31), Legal Events (4)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a division of application Ser. No. 595,901, filed Apr. 2, 1984 now U.S. Pat. No. 4,668,406.
This invention relates to the treatment of fibrous substrates, such as textile fibers, carpet, paper, and leather, with fluorochemicals to impart oil and water repellency, and to the resulting treated substrates. In another aspect, it relates to the treatment of carpet fiber with a finish comprising fluorochemicals to impart oil and water repellency and soil resistance to such fiber. In another aspect, it relates to fluoroaliphatic radical-containing compositions, solutions, dispersions, and emulsions, and their preparation, which are useful in such treatment.
In the industrial production of textile articles, such as carpet and apparel, and such other fibrous substrates as paper and leather, it is common to treat such substrates with fluorochemicals containing fluoroaliphatic radicals (often designated by the symbol "Rf ") to impart oil and water repellency to the surface of such substrates. Fluorochemicals of this type and their application to fibrous substrates are described in various prior art publications, e.g., U.S. Pat. Nos. 3,329,661 (Smith et al), 3,398,182 (Guenthner et al), 3,458,571 (Tokoli), 3,574,791 (Sherman et al), 3,728,151 (Sherman et al), 3,916,053 (Sherman et al), 4,144,367 (Landucci), 3,896,251 (Landucci), 4,024,178 (Landucci), 4,165,338 (Katsushima et al), 4,190,545 (Marshall), 4,215,205 (Landucci), 4,013,627 (Temple), 4,264,484 (Patel), 4,426,476 (Chang), 4,029,585 (Dettre), 3,462,296 (Raynolds et al), 4,401,780 (Steel), 4,325,857 (Champaneria et al), and Banks, R. E., Ed. "Organofluorine Chemicals and their Industrial Applications", Ellis Horwood, Ltd., West Sussex, England 226-230 (1979).
Although some fluorochemicals are useful in many applications and many are commercial products, some are relatively expensive to prepare and apply, others are difficult to apply, and others are not durable or do not impart the required properties to the extent desired.
Conventionally, fluorochemical compositions are applied to fibrous substrates, e.g., textiles and textile fiber, as solutions in organic solvents or as aqueous emulsions, as described in the above cited references, e.g., U.S. Pat. Nos. 3,329,661 and 4,024,178.
It is an object of this invention to provide a fluorochemical biuret and method for its preparation.
Another object of this invention is to provide fluorochemical biurets, including anionic and cationic derivatives thereof, useful for treating porous substrates, such as carpet fibers and carpet, for imparting oil, water and stain resistance thereto.
A further object of this invention is to provide fluorochemical biurets in the form of stable emulsions, microemulsions and dispersions useful for the treatment of porous substrates, such as fibers, paper, leather and the like to impart oil, water and stain resistance thereto.
A still further object of this invention is to provide blends of fluorochemical biurets and fluorochemical poly(oxyalkylenes), which blends can be used in the form of aqueous dispersions, emulsions and microemulsions to treat fibrous substrates such as textile fibers, filaments, yarns, or finished fibrous articles, such as carpet, and other fibrous substrates such as paper and leather, to impart oil and water repellency and stain resistance thereto.
This invention provides, in one aspect, fluorochemical biurets which have one or more monovalent fluoroaliphatic radicals (Rf), one or more biuret moieties ##STR1## and can contain organo amino or acid moieties, such as carboxylic, sulfonic and phosphorus acid moieties, and salts formed from the compounds containing the organo amino or acid moieties, such radicals and moieties being bonded together by hetero atom-containing or organic linking groups.
This invention also provides, in another aspect, blends of (a) the fluorochemical biuret, and (b) normally liquid or low melting solid, water soluble or dispersible, fluoroaliphatic radical-containing poly(oxyalkylenes).
The fluorochemical biuret and the blends of (a) the fluorochemical biuret and (b) the fluorochemical poly(oxyalkylene) are useful in the form of aqueous suspensions, emulsions, and microemulsions, and organic solutions in the treatment of fibrous substrates, such as textile fibers during manufacture, and useful also in the treatment of finished or fabricated fibrous substrates such as carpets, paper and leather, to impart oil and water repellency thereto.
A class of the fluorochemical biurets of this invention can be represented by the general formula I ##STR2## where each R1 is the same or different and is selected from hydrogen and terminal monovalent organic radicals such as alkyl, cycloalkyl, aryl, and combinations thereof, e.g. aralkyl, and can contain fluoroaliphatic radicals (Rf), for example from 1 to 20 Rf radicals, additional biuret moieties, for example, from 1 to 20 biuret moieties, and one or more hetero moieties, e.g. --O--, --S--, ##STR3## and --CO--, and is preferably free of active hydrogen atoms (i.e., hydrogen atoms of groups such as mercapto, amino, carboxyl, and aliphatic hydroxyl groups) that can readily react with isocyanate under urethane bond-forming conditions, e.g., 20� to 100� C., with the proviso that at least one R1 contains Rf , said R1 can also contain amino or acid groups. Said class also includes salts of the biurets containing the amino or acid groups.
A subclass of the fluorochemical biurets of formula I is represented by the general formula II ##STR4## where: B is a biuret moiety, ##STR5## A is a divalent organic linking group linking group which can contain an Rf group or additional biuret moieties; X is O, S or NR3, where R3 is H or lower alkyl having 1 to 4 carbon atoms; Q is a divalent linking group; R2 is selected from hydrogen, and terminal monovalent organic radicals such as alkyl, cycloalkyl, aryl and combinations thereof, e.g. aralkyl, which radicals can contain fluoroaliphatic radicals (Rf), additional biuret moieties, and hetero moieties, e.g. --O--, --S--, ##STR6## and --CO--, and is preferably free of active hydrogen atoms and may contain additional biuret moieties, each R2 or A being the same or different, with the proviso that there is at least one R2 or A containing at least one Rf, p is zero or 1, R6 is selected from hydrogen, lower alkyl groups having 1 to 4 carbon atoms, and aralkyl groups having 7 to 13 carbon atoms, E is an anion derived from a protonic acid or an alkylating agent selected from alkyl chloride, alkyl bromide, alkyl iodide, dimethyl sulfate, diethyl sulfate, formic acid, acetic acid, glycolic acid, and citric acid, a is zero or 1, and m is zero, 1 or 2.
Another subclass of the fluorochemical biurets of formula I is represented by formula III ##STR7## where A, B, X, Q, R2, and p are the same as in formula II; R4 is a monovalent or polyvalent organic linking group, preferably alkylene, G is an anionic terminal group selected from COOM1 /v, SO3 M1 /v, PO(OM1 /v)2, OSO3 M1 /v, and OPO(OM1 /v)2, where M is hydrogen or a cationic moiety, such as an alkali metal or an alkali earth metal, e.g., Na, K, and Mg, and amino salt groups, e.g., N(C2 H5)3 H, (CH3)2 NHC2 H4 NH(CH3)2, ##STR8## and v is the valence M, x is zero or 1, and y is 1 to 4, with the proviso that x+y is 1 to 4.
A further subclass of the fluorochemical biurets is represented by formula IV ##STR9## where A, B, X, R2, R4, G, x and y are the same as in formulas II and III.
In each of the above fluorochemicals, where there are a plurality of Rf, Q, A, R1 , R2, R3, R4 and X groups or moieties, each can be the same or different. Also, the biurets of formulas I-IV represent individual compounds or represent mixtures of such compounds, for example, as they are obtained as products from reactions used in their preparation. In addition, small amounts of by-products, with and without the fluoroaliphatic group Rf, and not represented by any of the formulas I-IV, can also be present in small amounts in said mixtures or reaction products because of the reaction conditions involved in their preparation. Such presence of such small amounts of by-products, generally less than 10 weight percent, does not affect the usefulness of the fluorochemical biuret mixtures or products of this invention.
The fluoroaliphatic radical, Rf, referred to above, is a fluorinated, stable, inert, non-polar, preferably saturated, monovalent moiety which is both oleophobic and hydrophobic. It can be straight chain, branched chain, or, if sufficiently large, cyclic, or combinations thereof, such as alkylcycloaliphatic radicals. The skeletal chain in the fluoroaliphatic radical can include catenary oxygen, hexavalent sulfur, and/or trivalent nitrogen hetero atoms bonded only to carbon atoms, such hetero atoms providing stable linkages between fluorocarbon portions of Rf and not interfering with the inert character of the Rf radical. While Rf can have a large number of carbon atoms, compounds where Rf is not more than 20 carbon atoms will be adequate and preferred since large radicals usually represent a less efficient utilization of fluorine than is possible with smaller Rf radicals. Generally Rf will have 3 to 20 carbon atoms, preferably 6 to about 12, and will contain 40 to 78 weight percent, preferably 50 to 78 weight percent, fluorine. The terminal portion of the Rf group has at least three fully fluorinated carbon atoms, e.g., CF3 CF2 CF2 -- and the preferred compounds are those in which the Rf group is fully or substantially completely fluorinated, as in the case where Rf is perfluoroalkyl, Cn F2n+ 1.
The function of the linking group Q in the above formulas is to bond the R2 group, as in formulas II and III, directly to A and X groups or indirectly to A and X groups through hetero atom-containing moieties. Each Q can comprise a hetero atom-containing group or an organic group or a combination of such groups, examples of which are polyvalent aliphatic, e.g., --CH2 --, --CH2 CH2 --, and --CH2 CH(CH2 --)2, polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, --N(CH3)--, sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, carbonyloxy, urethane, e.g., --CH2 CH2 OCONH--, and urylene, e.g., --NHCONH--. The linkage Q for a specific fluorochemical biuret useful in this invention will be dictated by the ease of preparation of such a compound and the availability of necessary precursors thereof. However, the Q group is preferably free of active (or isocyanate-reactive) hydrogen atoms, i.e., hydrogen atoms of groups such as mercapto, amino, carboxyl, and aliphatic hydroxyl groups that can react readily with isocyanate groups under urethane bond-forming conditions, e.g., 20�-100� C.
The divalent organic linking group A in formulas II, III, and IV above illustratively are alkylene groups, such as ethylene, isobutylene, hexylene, and methylenedicyclohexylene, having 2 to about 20 carbon atoms, aralkylene groups, such as --CH2 C6 H4 CH2 -- and --C6 H4 CH2 C6 H4 --, having up to 20 carbon atoms, arylene groups, such as tolylene and various combinations of these groups. Such groups can also include from 1 to 10 Rf, from 1 to 10 biuret moieties and other hetero atom containing moieties, including --O--, --S--, and ##STR10## e.g., --(C2 H4 O)2 C2 H4 --, where z is 1 to about 5. However, A is preferably free of groups with active hydrogen atoms.
The A group can be a residue of an organic diisocyanate from which the biuret, urethane, urylene and other isocyanate-derived moieties arise, that is, A can be the divalent radical obtained by removal of the isocyanate groups from an organic diisocyanate. Suitable diisocyanate precursors may be simple, e.g., hexamethylene diisocyanate, xylylene diisocyanate, tolylene-2,4-diisocyanate, methylene bis(4-phenyleneisocyanate), and mixtures thereof, or complex, as formed by the reaction of a simple diisocyanate with an organic diol or polyol in appropriate proportions to yield an isocyanate-terminated polyurethane. Other isocyanates can also be used as starting materials. Some of these are described, for example, in U.S. Pat. No. 4,174,433. Representative A groups include --CH2 C6 H4 CH2 C6 H4 CH2 --, --C6 H10 CH2 C6 H10 --, --(CH2)6 --, C6 H4 --, C8 F17 SO2 NHC2 H40 CONHC6 H3 (CH3)2 --, --C6 H4 C8 F17 SO2 N(C2 H5)C2 H40 CONHC6 H12 N(CONHC6 H12 --2 --, and --(CH2)6 [NHCOO(CH2)40 CONH(CH2)6 C2.
Generally, the fluorochemical biurets of this invention will contain about 20 to 70 weight percent, preferably about 25 to 50 weight percent, of carbon-bonded fluorine. If the fluorine content is less than about 20 weight percent, impractically large amount of the fluorochemical biuret compounds will generally be required, while fluorine contents greater than about 70 weight percent are unnecessary to achieve the desired surface properties and thus represent an uneconomical use of fluorine.
The fluorochemical biurets of this invention can be derived from fluorine-free isocyanate-functional biurets, the latter reagents being conveniently prepared by the reaction of a diisocyanate with water as described in U.S. Pat. No. 3,124,605. A commercial biuret triisocyanate product, "Desmodur" N-100 , has the principle structure ##STR11##
In preparing the fluorochemical biuret of this invention, a isocyanate-functional biuret, e.g., "Desmodur" N-100 , can be reacted with a Rf -containing reagent, e.g., those containing isocyanate-reactive hydroxyl, mercapto, or amino groups. Coreactants selected from fluorine-free, isocyanate-reactive hydroxyl, mercapto and amino compounds can also be used.
Representative reaction schemes for the preparation of fluorochemical biurets of this invention are outlined below. In these schemes, a portion of the Rf --Q--X--H reactant can be replaced by R--Q--X--H where R is an organic radical as defined for R1, preferably an alkyl. radical. ##STR12##
The product of Scheme 2 may then be reacted with an amine or other base to form a salt of the product. ##STR13##
The product of Scheme 3 may then be reacted with an acid or alkylating agent to form a salt of the product. ##STR14##
The fluorochemical biurets can also be prepared from Rf -containing isocyanates or amines in biuret-forming reactions. These are illustrated in the following schemes. ##STR15##
Representative Rf intermediates for the preparation of the fluorochemical compositions of this invention include: C8 F17 SO2 N(C2 H5)C2 H4 OH, C8 F17 C2 H4 OH, C7 F15 CH2 OH, C7 F15 CON(C2 H5)C2 H4 OH, C8 F17 C2 H4 SC2 H4 OH, (CF3)2 CF(CF2)8 C2 H4 OH, (CF3)2 CFOC2 F4 C2 H4 OH, C8 F17 C2 H4 SO2 ##STR16##
Representative organic isocyanates include tolylene-2, 4-diisocyanate, hexamethylene diisocyanate, methylenebis (4-phenyleneisocyanate), methylenebis (4-cyclohexyleneisocyanate), xylylene diisocyanate, 1 -methoxy-2, 4-phenylene diisocyanate, p-(1-isocyanatoethyl)phenyl isocyanate, phenyl isocyanate, m-tolyl isocyanate, 2,5-dichlorophenyl isocyanate, hexyl isocyanate, and isophorone diisocyanate, and mixtures thereof.
Representative isocyanate-reactive alcohol, mercapto, and amine reagents include ethylene glycol, 1,3-propanediol, 1,4-butanediol, glycerine, 1,1,1-trimethylolpropane, 1,3-dihydroxy-2-propane, 3 3-mercapto-1,2-propanediol, 2-aminoethanol, -amino-1-propanol, 1,4-diaminobutane, 1,6-diaminohexane, N(3-aminopropyl)diethanolamine, 3-amino-1,2-propanediol, triethylenetetramine, 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-diisopropylaminoethanol, N-methyldiethanolamine, triethanolamine, 1-methyl-3-pyrrolidinol, 2(2-hydroxyethyl)pyridine, N(2-hydroxyethyl)morpholine, 1,4-bis(2-hydroxypropyl)piperazine, 1,1-dimethyl-4-dimethylamino-n-butanol, N(2-hydroxyethyl)pyrrolidine, 1-methyl-3-piperidinol, N(2-hydroxyethyl)-N-methylaniline, 2-dimethylaminoethanethiol, N,N-bis(2-mercaptoethyl)methylamine, 4-diethyl-amino-1-methyl-n-butanol, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 3-dimethylamino-2-hydroxy-n-propanol, N,N-dimethyl-1,3-propanediamine, N(2-amino- ethyl)-morpholine, 4(2-aminoethyl)-pryridine, and tris(2-aminoethyl)-amine, ethanol, octanol, octadecanol, hexylamine, dibutylamine, dodecylmercaptan, and mixtures thereof.
Representative hydroxy, mercapto and amino-group containing acids include 2,2-bis(hydroxymethyl)propionic acid, glycolic acid, 3-hydroxypropionic acid, glycine, 4-aminobutyric acid, mercaptoacetic acid, citric acid, malic acid, 3-aminopropane sulfonic acid, 4-hydroxybenzene sulfonic acid, 1,3-dihydroxybenzene sulfonic acid, and mixtures thereof.
Quaternizing alkylating agents and acids useful in this inventon include: methyl iodide, methyl bromide, allyl chloride, benzyl chloride, diethylsulfate, dimethylsulfate, bis(trifluoromethyl) sulfate, epichlorohydrin, hydrochloric acid, acetic acid, formic acid, and glycolic acid.
The fluoroaliphatic radical-containing poly(oxyalkylenes), called fluorochemical oxyalkylenes for brevity, used as component (b) in the fluorochemical blends of this invention are normally liquid or low melting solids. They contain one or more Rf groups (as defined above), and one or more poly(oxyalkylene) moieties bonded together by hetero atom-containing or organic linking groups, or combinations of such groups.
A class of fluorochemical oxyalkylene used in this invention are fluoroaliphatic polymers (or oligomers, the term polymer hereinafter including oligomer unless otherwise indicated) represented by the general formulas:
(Rf)s Z[(R5)r Z'Y]t IV
(Rf)s Z[(R5)r Z'Y']tw V
Rf is a fluoroaliphatic radical like that described above,
Z is a linkage through which Rf and (R5)r moieties are covalently bonded together,
(R5)r is a poly(oxyalkylene) moiety, R5 being an oxyalkylene group with 2 to 4 carbon atoms and r is an integer (where the above formulas are those of individual compounds) or a number (where the above formulas are those of mixtures) at least 5 ) , generally 10 to 75 and can be as high as 100 or higher,
Y is a hydrogen atom or a monovalent terminal organic radical,
Y' is Y or a valence bond, with the proviso that at least one Y' is a valence bond connecting a Z-bonded R5 radical to another Z,
Z' is a linkage through which Y, or Y', and R5 are covalently bonded together,
s is an integer or number of at least 1 and can be as high as 25 or higher,
t is an integer or number of at least 1 , and can be as high as 60 or higher, and
w is an integer or number greater than 1, and can be as high as 30 or higher.
In formulas IV and V, where there are a plurality of Rf radicals, they are either the same or different. This also applies to a plurality of Z, Z', R5, Y, Y', and, in formula V, a plurality of r, s, and t.
Generally, the oxyalkylene polymers will contain about 5 to 40 weight percent, preferably about 10 to 30 weight percent, of carbon-bonded fluorine. If the fluorine content is less than about 10 weight percent, impractically large amounts of the polymer will generally be required, while fluorine contents greater than about 35 weight percent result in polymers which have too low a solubility to be efficient.
In the poly(oxyalkylene) radical, (R5 )r, R5 is an oxyalkylene group having 2 to 4 carbon atoms, such as --OCH2 CH2 --OCH(CH3)CH(CH3)--, the oxyalkylene units in said poly(oxyalkylene) being the same, as in poly(oxypropylene), or present as a mixture, as in a heteric straight or branched chain or randomly distributed oxyethylene and oxypropylene units or as in a straight or branched chain of blocks of oxyethylene units and blocks of oxypropylene units. The poly(oxyalkylene) chain can be interrupted by or include one or more catenary linkages. Where said catenary linkages have three or more valences, they provide a means for obtaining a branched chain or oxyalkylene units. The poly(oxyalkylene) radicals in the polymers can be the same or different, and they can be pendent. The molecular weight of the poly(oxyalkylene) radical can be as low as 200 but preferably is about 500 to 5,000.
The function of the linkages Z and Z' is to covalently bond the fluoroaliphatic radicals, Rf, the poly(oxyalkylene) moieties, (R5)r and radicals Y and Y' together in the oligomer. Z and Z' can be a valence bond, for example where a carbon atom of a fluoroaliphatic radical is bonded or linked directly to a carbon atom of the poly(oxyalkylene) moiety. Z and Z' each can also comprise one or more linking groups such as polyvalent aliphatic and polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, phosphoxy, amine, and combinations thereof, such as oxyalkylene, iminoalkylene, iminoarylene, sulfoamido, carbonamido, sulfoamidoalkylene, carbonamidoalkylene, urethane, urea, and ester. The linkages Z and Z' for a specific oxyalkylene polymer will be dictated by the ease of preparation of such a polymer and the availability of necessary precursors thereof.
From the above description of Z and Z', it is apparent that these linkages can have a wide variety of structures, and in fact where either is a valence bond, it doesn't even exist as a structure. However large Z and Z are, the fluorine content (the locus of which is Rf is in the aforementioned limits set forth in the above description, and in general the sum of Z and Z' contents of the polymer is preferably less than 10 weight percent of the polymer.
The monovalent terminal organic radical, Y, is one which is covalently bonded through Z' to the poly(oxyalkylene) radical. Though the nature of Y can vary, it preferably is such that it compliments the poly(oxyalkylene) moiety in maintaining or establishing the desired solubility of the oxyalkylene. The radical Y can be a hydrogen atom, acyl, such as C6 H5 C(O)--, alkyl, preferably lower alkyl, such as methyl, hydroxyethyl, hydroxypropyl, mercaptoethyl and aminoethyl, or aryl, such as phenyl, chlorophenyl, methoxyphenyl, nonylphenyl, hydroxyphenyl, and aminophenyl. Generally, ZY will be less than 50 weight percent of the (R5 )r Z'Y moiety.
The fluoroaliphatic radical-containing poly(oxyalkylene) used in this invention can be prepared by a variety of known methods, such as by condensation, free radical, or ionic homopolymerization or copolymerization using solution, suspension, or bulk polymerization techniques, e.g., see "Preparative Methods of Polymer Chemistry", Sorenson and Campbell, 2nd ed., Interscience Publishers, (1968). Classes of representative poly(oxyalkylenes) useful in this invention include polyesters, polyurethanes, polyepoxides, polyamides, and vinyl polymers such as polyacrylates and substitute polystyrenes.
The polyacrylates are a particularly useful class of poly(oxyalkylenes) and they can be prepared, for example, by free radical initiated copolymerization of a fluoroaliphatic radical-containing acrylate with a poly(oxyalkylene) acrylate, e.g., monoacrylate or diacrylate or mixtures thereof. As an example, a fluoroaliphatic acrylate, Rf R"--O2 C--CH=CH2 (where R" is, for example, sulfonamidoalkylene, carbonamidoalkylene, or alkylene), e.g., C8 F17 SO2 N(C4 H9)CH2 CH2 O2 CCH=CH2) , can be copolymerized with a poly(oxyalkylene) monoacrylate, CH2 =CHC(O)(R5 )x OCH3, to produce a polyacrylate oxyalkylenes.
Further description of fluorochemical oxyalkylenes useful in this invention will be omitted in the interest of brevity since such compounds and their preparation are known, and are described in U.S. Pat. No. 3,787,351 and U.S. Pat. No. 4,289,892, both of which are incorporated herein by reference.
The relative amounts of component (a), the fluorochemical biurets, and component (b), the fluorochemical poly(oxyalkylene), in the fluorochemical blend used in this invention to treat porous, fibrous substrates can vary over a broad range and will be selected to provide the desired balance of surface properties on the treated fiber of the finished article. Generally, component (a) will be the major amount of the blend and component (b) will be the minor amount. The particular amount depends on the particular composition of the textile fiber or article to be treated and the particular chemical composition of (a) and (b), as well as the application procedures used.
Generally, the relative amounts of components (a) and (b) fall within the following ranges:
______________________________________Amount of fluorochemical solids in blend (wt. %) General Preferred MostComponent Broad Range Broad Range Preferred Range______________________________________(a) 40 to 99 60 to 99 70 to 95(b) 1 to 60 1 to 40 5 to 30______________________________________
The fluorochemical biurets of this invention, and blends thereof with fluorochemical poly(oxyalkylenes) can be utilized as solutions in organic solvents or as aqueous emulsions or dispersions. Aqueous emulsions and microemulsions are particularly useful forms for the fluorochemical biurets and the blends thereof with poly(oxyalkylenes) of this invention because of the ease of formation and stability of these emulsions, especially when a salt forming moiety is present in the fluorochemical biuret compositions.
In the preparation of these aqueous emulsions, it is generally beneficial in ease of formation and particularly in emulsion stability to include a nonionic surfactant, thus the blends of this invention comprising (a) the fluorochemical biuret and (b) fluorochemical poly(oxyalkylenes) yield emulsions and microemulsions having excellent properties. Also these blends generally yield improved oil and water repellency when applied to porous substrates, e.g., carpet fibers and carpets.
Hydrocarbon nonionic surfactants are also beneficial in forming stable emulsions and microemulsions. These can be used in place of the fluorochemical nonionic surfactants, i.e., the fluorochemical poly(oxyalkylenes) or in addition to them as a co-surfactant. Hydrocarbon and fluorochemical anionic and cationic surfactants may also be beneficial as co-surfactants with the hydrocarbon and fluorochemical nonionic surfactants.
Representative hydrocarbon surfactants and co-surfactants useful in this invention include the following commercial poly(oxyalkylene) compounds: poly(oxyethylene) sorbitan monooleate, e.g., "Tween"80; alkylaryl polyethylene glycol ether, e.g., "Surfonic" N-120; ethoxylated lauryl alcohol, e.g., "Siponic" L-16; octylphenoxy polyethoxy ethanol, e.g., "Triton" X-102; polyethylene glycol ether of sec. alcohol, e.g., "Tergitol" 15-S-15; poly(oxyethylene) cetyl ether, e.g., "Brij" 58; octylphenoxypoly(oxyethylene) ethanol, e.g., "Igepal" CA 720, sodium lauryl sulfate, e.g. "Dupanol" QC.
Each of these surfactants and co-surfactants has a hydrophile-lipophile balance value in the range of about 12 to 18. Those hydrocarbon poly(oxyalkylenes) with higher or lower values were found not to be as useful in promoting emulsion stability and quality, but may be useful in surfactant blends.
Substrates which can be treated in accordance with this invention are textile fibers (or filaments), and finished or fabricated fibrous articles such as textiles, e.g., carpet, paper, paperboard, leather, and the like. The textiles include those made from natural fibers, such as cotton and wool and those made from synthetic organic fibers, such as nylon, polyolefin, acetate, rayon, acrylic, and polyester fibers. Especially good results are obtained on nylon and polyester fibers. The fibers or filaments as such or in an aggregated form, e.g., yarn, tow, web, or roving, or the fabricated textile, e.g., articles such as carpet and woven fabrics, can be treated with the fluorochemical biuret or blends thereof with poly(oxyalkylenes). The treatment can be carried out by applying the fluorochemical biuret composition or blends as organic solutions or aqueous or organic dispersions by known techniques customarily used in applying fluorochemicals, e.g., fluorochemical acrylate copolymers, to fibers and fibrous substrates. If desired, such known fluorochemicals as fluoroaliphatic radical-containing polymers, e.g., acrylates and methacrylates can be used in conjunction with the above-described fluorochemical biuret blends. For example, the fluorochemical treatment, with the fluorochemical being in the form of an aqueous emulsion or organic solution, can be carried out by immersing the fibrous substrates in a bath containing the cationic fluorochemical blends, padding the substrate or spraying the same with the fluorochemical emulsions or solutions, or by foam, kiss-roll, or metering applications e.g., spin finishing, and then drying the treated substrates if solvent is present. If desired, the fluorochemical composition or blends can be co-applied with conventional fiber treating agents, e.g., antistatic agents or non-aqueous fiber lubricants.
In the manufacture of synthetic organic fibers (see, for example, the review article in Kirk-Othmer, Encyclopedia of Polymer Science and Technology, 8, 374-404 1968), the first step that normally takes place in the process, following initial formation of the filaments (e.g., by melt spinning or solvent spinning), is coating the fiber surface with a small amount of fiber finish comprising lubricating and antistatic agents. It is particularly advantageous to treat such fibers, e.g., nylon 66 and nylon 6, with the fluorochemical biurets or blends thereof of this invention in conjunction with the spin finish being applied to such textile fibers.
Fiber finishes are generally produced in the form of dilute aqueous emulsions or as non-aqueous solutions, or dispersions, which principally contains said lubricant and antistatic agents as well as emulsifier (surfactant) and may also contain materials such as bactericides and antioxidants.
Representative lubricants include mineral oils, waxes, vegetable oils (triglycerides) such as coconut oil, peanut oil, and castor oil, synthetic oils, such as esters, polyoxyethylene derivatives of alcohols and acids, and silicone oils.
The antistatic agents, emulsifiers, and surfactants which can be incorporated into the fiber finish are selected from similar chemical classes, which include:
(a) anionics, such as fatty acid soaps, sulfated vegetable oils, salts of alkyl and ethoxylated alkyl phosphates;
(b) cationics, such as fatty amines, quaternary ammonium compounds, and quaternary phosphonium compounds;
(c) nonionics, such as glyceryl monooleate, ethoxylated alcohols, ethoxylated fatty acids, and ethoxylated fatty amides; and
(d) amphoterics, such as betaines, amino acids and their salts.
A preferred method of applying the fluorochemical biuret composition blends of this invention to synthetic organic fibers is to incorporate the blend into the above-described fiber finishes in an amount sufficient to achieve the desired properties, oil and water repellency and soil resistance. Generally, the amount of fluorochemical to be used will be that sufficient to retain on the fiber of the finished article, e.g., carpet, about 200 to 1600 ppm fluorine based on the weight of the fiber. Such additions to the conventional fiber finish can be carried out without sacrificing or adversely affecting typical requirements that conventional fiber finishes must meet, namely lubrication, thermal stability, low fuming at elevated temperature, and wetting for fiber dyeability (color addition). The conventional finish components of the fiber finishes containing the fluorochemical biurets and blends thereof of this invention can be removed in a conventional manner after the fiber is manufactured in fiber form, e.g., carpets and upholstery fabrics. The fluorochemical biurets and blends thereof withstand the typical conditions encountered during fiber and yarn processing and also survive the more severe processing conditions which the greige goods encounter such as scouring and dyeing, and the finished goods encounter, such as washing, steam cleaning, and dry cleaning. The fluorochemical biurets and blends thereof do not interfere with, and are durable through, the normal fiber processing steps, e.g., drawing, texturizing, and heat setting, and provide oil and water repellency and anti-soiling properties to the finished article, e.g. carpet made from the treated fibers.
The conventional application methods used to apply finishes to fibers (or filaments) can be used with the fluorochemical biurets or blends thereof of this invention. Such methods include the use of either (a) a revolving ceramic cylinder, i.e., kiss-roll, which is partially immersed in a pan containing the fluorochemical finish, over which the moving filaments pass and pick up a thin film of finish, (b) a metering pump supplying finish through a slot or hole in a fiber guide over which the moving filaments pass, (c) an immersion finish bath, or (d) spraying devices.
Representative fluorochemical oxyalkylenes useful as component (b) in the fluorochemical blends of this invention are shown in Table 4. Generally, the preparation of the fluorochemical oxyalkylenes results in products which comprise mixtures of oxyalkylenes, the lengths of the fluoroaliphatic radical and the poly(oxyalkylene) moiety varying and the subscripts denoting the number of carbon atoms of the former and denoting the number of oxyalkylene units in a poly(oxyalkylene) segment being in both cases average numbers, and in this specification, e.g., Table 4, those subscripts should be understood as having such average values, unless otherwise indicated.
Representative fluorochemical oxyalkylene polyacrylates useful as component (b) in the blends of this invention are those made by copolymerizing any of the fluorochemical acrylates of Table 5 with any of the fluorine-free poly(oxyalkylene) monomers of Table 6.
TABLE 5______________________________________1. C8 F17 SO2 N(CH3)CH2 CH2 OCOCHCH242. C6 F13 C2 H4 OCOC(CH3)CH23. C6 F13 C2 H4 SC2 H4 OCOCHCH24. C8 F17 C2 H4 OCOC(CH3)CH25. C8 F17 C2 H4 N(CH3)C2 H4 OCOC(CH.sub.3)CH26. C2 F5 C6 F10 CH2 OCOCHCH27. C7 F15 CH2 OCOCHCH28. C7 F15 CON(CH3)C2 H4 OCOCHCH29. (CF3)2 CF(CF2)6 CH2 CH(OH)CH2 OCOCHCH.sub.210. (CF3)2 CFOC2 F4 C2 H4 OCOCHCH211. C8 F17 C2 H4 SO2 N(C3 H7)C2H4 OCOCHCH212. C7 F15 C2 H4 CONHC4 H8 OCOCHCH2 ##STR19##14. C7 F15 COOCH2 C(CH3)2 CH2 OCOC(CH3)CH215. C8 F17 SO2 N(C2 H5)C4 H8 OCOCHCH.sub.216. (C3 F7)2 C6 H3 SO2 N(CH3)C2H4 OCOCHCH2 ##STR20##18. C6 F13 CFCHCH2 N(CH3)C2 H4 OCOCHCH.sub.219. C8 F17 SO2 N(C4 H9)C2 H4 OCOCHCH.sub.220. C8 F17 SO2 N(C2 H5)C2 H4 OCOCH(CH.sub.3)CH2______________________________________
TABLE 6______________________________________ ##STR21##2. CH2 ═CHCO2 (C2 H4 O)17 CH33. CH2 ═C(CH3)CONH(C3 H6 O)44 H4. CH2 ═C(CH3)CO2 (C2 H4 O)90 COC(CH.sub.3)═CH25. HS(C2 H4 O)23 (C3 H6 O)35 (C2H4 O)22 C2 H4 SH______________________________________
Representative compounds of this invention were prepared from the reactants listed in Table 1, following the procedures set forth in Examples 1 and 2, with stoichiometry and structures summarized in Tables 2 and 3, respectively.
TABLE 1______________________________________Code Reactant formula______________________________________A1 C8 F17 SO2 N(C2 H5)C2 H4 OHA2 C8 F17 SO2 N(CH3)C2 H4 OCH2 CH(CH2 Cl)OHA3 C7 F15 C2 H4 OHA4 C8 H17 OHA5 C2 H5 C(CH2 OH)3 ##STR22##C CH3 C(CH2 OH)2 COOHD1 N(CH2 CH2 OH)3D2 H2 N(CH2)6 NH2D3 N(C2 H5)3E ##STR23##F HCOOHG (C2 H5)2 SO4H H2 NC3 H6 SO3 H______________________________________
In a one liter, 3-neck flask fitted with a mechanical stirrer, thermometer, condenser, gas inlet tube, addition funnel and electric heating mantle was placed 164g (0.34 mole) "Desmondur" N-100 biuret triisocyanate, and 109g ethyl acetate and 4 drops stannous octoate. The mixture was heated to 82� C. and stirred under a slow N2 stream while slowly adding over a period of 3 hours a solution of 319g (0.55 mole) N-ethyl (perfluorooctane) sulfonamidoethyl alcohol in 212g ethyl acetate and containing 3 drops of stannous octoate. Heating (82� C.) and stirring was continued for a period of 3 hours to yield mainly a fluorochemical biuret urethane isocyanate intermediate, (C8 F17 SO2 N(C2 H5)C2 H4 OCONHCO--2 NC6 H12 NCO or more simply (Rf --Q--A--2 B--A--NCO, and smaller amounts of B--A--Q--Rf)3 and (OCN--A--.sub. B--A--Q--Rf with B, A, Q and Rf as defined above.
The temperature was lowered to 70� C. and 17.3g (0.116 mole) tris(2-hydroxyethyl) amine was added, the temperature raised to 82� C., and heating and stirring continued for an additional 1.5 hours.
Infrared absorption analysis of a small portion of reaction mixture indicated that all of the isocyanate groups had been converted to urethane groups to yield a mixture of fluorochemical biurets of composition 1 in Table 2, as the principal product.
The above biuret urethane solution (417g) was combined with 262g of additional ethyl acetate, 988g of distilled water, 38g "Tergitol" 15-S-40 nonionic surfactant and 5g of a fluorochemical poly(oxyalkylene), a copolymer of C8 F17 SO2 N(CH3)C2 H4 OCOCH═CH2, CH2 ═C(CH3)COO(CH2 CH2 O)90 H and CH2 ═C(CH3)COO(CH2 CH2 O)90 COC(CH3)═CH2, and the mixture stirred and heated at 70� C. for 20 minutes, then subjected to two passes through a high shear homogenizer. The resulting emulsion was stripped of ethyl acetate (to less than 1% as measured by gas chromatography) at reduced pressure with a water aspirator and a pot temperature of up to 55� C. to yield an aqueous emulsion with 18.3% fluorochemical solids (21% total solids).
This example describes the preparation of an anionic biuret urethane of this invention.
Following the general procedure of Example 1, N-ethyl(perfluorooctane) sulfonamidoethyl alcohol (1269g, 2.2 moles) and "Desmondur" N-100 (653g, 1.37 moles were reacted at 82� C. in ethyl acetate solution using stannous octoate catalyst to yield mainly a fluorochemical biuret urethane isocyanate intermediate, OCN--A--B--A--Q--Rf)2, with some B--A--Q--Rf)3 product.
The temperature was lowered to 70� C., 30.9g (0.23 mole) 1,1,1-trimethylol propane and 46.8 g (0.35 mole) 2,2-di(hydroxymethyl) propionic acid were added, the temperature raised to 82� C. and stirring and heating continued for 3 hours. Infrared absorption analysis of a small portion of the reaction mixture indicated complete reaction of the isocyanate groups to yield the fluorochemical anionic buiret urethane composition comprising a mixture of products: b, c, d and e (structures in Table 3) in a molar ratio of about 2:1:1:1, respectively.
The triethylamine salt was prepared by adding 35.2g (0.35 mole) triethylamine to the above reaction mixture and heating at 70� C. for 2 hours to yield the biuret salt mixture of composition 2 of Table 2.
An aqueous emulsion of the above fluorochemical biuret salt product, containing 21.2% fluorochemical solids (24.3% total solids) and less than one percent ethyl acetate was prepared following the procedure of Example 1 using the same nonionic emulsifiers.
Following the general procedures of Examples 1 and 2, and using the reactants shown in Tables 1 and 2, additional fluorochemical biuret compositions and emulsions were prepared. Molar ratios of reactants are indicated in Table 2, and product compositions and structures are indicated in Tables 2 and 3.
TABLE 2__________________________________________________________________________ Reactants (moles)*** Fluorochemical Amino or Acid, alkaline orEx. biuret Fluorochemical Aliphatic hydroxy Amino quaternizingNo. composition** Biuret alcohol alcohol acid alcohol Diamine agent__________________________________________________________________________1 a,c B(3) A1(6) D1(1)2 b,c,d,e* B(12) A1(24) A5(2) C(3) D3(3)3 a,f,k B(5) A1(10) D1(1) D2(1)4 g,c* B(2) A1(4) C(1) E(1)5 c B(1) A2(3)6 i B(7) A2(12) A5(3)7 c B(1) A1(3)8 c B(1) A3(3)9 j B(1) A3(2) A4(1)10 i B(3) A1(5) H(1) D1(1)11 a* B(3) A1(6) D1(1) F(1)12 a* B(3) A1(6) D1(1) F(0.33)13 a* B(3) A1(6) D1(1) G(1)14 a* B(3) A1(6) D1(1) G(0.33)__________________________________________________________________________ *Salt or quaternized derivatives of compound of Table 3 **The fluorochemical product compositions are generally mixtures, the likely principal product(s) being shown in simplified form in Table 3, where B, A, Q and Rf are as defined above. ***Reactant structure are shown in Table 1; moles shown in parenthesis ar relative
TABLE 3______________________________________(a) ##STR24##(b) ##STR25##(c) B(AQRf)3(d) ##STR26##(e) ##STR27##(f) ##STR28##(g) ##STR29##(h) ##STR30##(i) ##STR31##(j) RAB(AQRf)2(k) ##STR32##______________________________________
In these examples, several of the fluorochemical biurets of this invention, specified in Table 4, were used in the form of aqueous emulsions, in the presence of a nonionic textile fiber lubricant (1% SOF), and in combination with one or more nonionic surfactants, to treat samples of scoured nylon 66 greige carpet (28 oz/yd2) in a padding application (71% wet pickup).
The fluorochemical treated carpet samples were placed on a paper blotter to remove excess emulsion, then dried in a circulating air oven (25 minutes at 70� C. and 5 minutes at 150� C.).
The fluorochemical treated, dried samples were then acid dyed, excess aqueous dye solution removed, samples rinsed and dried at 70� C. and then heated for 5 minutes at 130� C.
The fluorochemical treated carpet samples were analyzed for fluorine before and after dyeing to measure retention of fluorochemical on the carpet fibers. The fluorochemical treated, dyed samples were evaluated for oil repellency (OR), water repellency (WR) and walk-on soil resistance (WOS). The results are summarized in Table 4.
The water repellency test is one which is often used for this purpose. The water repellency of treated samples is measured using a water/isopropyl alcohol test, and is expressed in terms of a water repellency rating (0-10) of the treated carpet or fabric. Treated carpets which are penetrated by or resistant only to a 100 percent water/0 percent isopropyl alcohol mixture (the least penetrating of the test mixtures) are given a rating of 0, whereas treated fabrics resistant to a 0 percent water/100 percent isopropyl alcohol mixture (the most penetrating of the test mixtures) are given a rating of 10. Other intermediate values are determined by use of other water/isopropyl alcohol mixtures, in which the percentage amounts of water and isopropyl alcohol are each multiples of 10. The water repellency rating corresponds to the most penetrating mixture which does not penetrate or wet the fabric after 10 seconds contact. In general, a water repellency rating of 1 or 2, is desirable for carpet.
The oil repellency test is also one which is often used for this purpose. The oil repellency of treated carpet and textile samples is measured by AATCC Standard Test 188-1978, which test is based on the resistance of treated fabric to penetration by oils of varying surface tensions. Treated fabrics resistant only to "Nujol", a brand of mineral oil and the least penetrating of the test oils, are given a rating of 1, whereas treated fabrics resistant to heptane (the most penetrating of the test oils) are given a value of 8. Other intermediate values are determined by use of other pure oils or mixtures of oils. The rated oil repellency corresponds to the most penetrating oil (or mixture of oils) which does not penetrate or wet the fabric after 10 seconds contact rather than the 30 seconds contact of the Standard Test. Higher numbers indicate better oil repellency. In general, an oil repellency of 2 or greater is desirable for carpet.
The soil resistance of treated and untreated (control) carpet was determined by exposure to pedestrian traffic according to AATCC Test method 122-1979, the exposure site being a heavily travelled industrial area for an exposure of about 15,000 "traffics". The samples are repositioned periodically to insure uniform exposure and are vacuumed every 24 hours during the test and before visual evaluation. The evaluation employed the following "Walk-On-Soiling" (WOS) rating system:
______________________________________WOSRating Description______________________________________ 0 equal to control�1/2 slightly better (+) or worse (-) than control�1 impressive difference compared to control �11/2 very impressive difference compared to control�2 extremely impressive difference compared to control______________________________________
In the tables which follow, the surfactant used is identified according to the following code:
______________________________________Code Surfactant______________________________________A "Tergitol" 15-S-40B poly(oxyalkylene) copolymer of C8 F17 SO2 N(CH3)C2 H4 OCOCH═CH.su b.2, CH2 ═C(CH3)COO(CH2 CH2 O)90 H, and CH2 ═C(CH3)COO(CH2 CH2 O)90 COC(CH3)═CH2C "Triton" X-405D "Triton" X-102E C8 F17 SO2 N(C2 H5)CH2 COOKF C8 F17 SO2 NHC3 H6 N(CH3)3 ClG "Tween" 80H "Tergitol" 15-S-30I "Dowfax" 2A1______________________________________
TABLE 4__________________________________________________________________________Fluorochemical compositions Properties of treated carpetFluorochemical Aqueous emulsion PercentEx. Identity Surfactant % fluorochemical fluorochemical retentionNo. Table 2 No. Code %* solids through dyeing OR WR WOS__________________________________________________________________________11 1 A,B 15,2 18 84 5 6 +11/412 2 A,B 13,2 21 85 6 4 +11/213 3 C,D 15,3 17 100 5 7 +11/214 4 A,E 15,2 19 57 4 5 +13/415 5 A,E 15,2 18 -- 4 7 +11/216 6 B 17,5 19 -- 4 7 +11/217 7 H,I 10,5 19 100 4 3 +3/418 8 F,G 2,13 16 69 6 8 --19 9 F,G 2,13 16 77 6 6 --20 10 B,G 2,13 17 73 5 6 --21 11 A,B 15,2 18 98 5 8 +11/222 12 B,F,G 35,1,6 23 93 6 9 +3/423 13 A,B 15,2 18 94 5 8 +124 14 B,F,G 35,1,6 22 76 5 8 +11/4Control -- -- 0 -- 0 NWR** 0__________________________________________________________________________ *Percent with respect to fluorochemical biuret **NWR means no waterrepellency
The test data show that nylon carpet pad-treated with the fluorochemical biuret has good oil and water repellency and soil resistance and that the fluorochemical biuret is retained on the carpet through the dyeing process.
Example 25 describes the treatment of nylon carpet fiber with 0.2% (baed on %F) aqueous emulsions of a fluorochemical biuret of composition No. 2 of Table 2, in combination with a 3.5 wt. % aqueous emulsion of a coconut oil-based fiber spin finish, and a fluorochemical oxyalkylene and hydrocarbon nonionic surfactant, as indicated in Table 5.
The fluorochemical spin finish emulsion composition adjusted to 0.2% fluorochemical (based on F content) was applied by a metered slot applicator to melt extruded, undrawn yarn of nylon 66. The yarn was made of 100 filaments of 20 denier (per filament). The treated yarn was continuously drawn and texturized and made into level-loop carpet (28 oz./yd2), heat set at 190� C. for one minute, acid dyed, dried at 70� C. for 30 min., heated at 130� C. for 10 min., and then evaluated, together with an untreated control, Example 26, for oil and water repellency, walk-on soil resistance, and retention of fluorochemical through the dyeing process as determined by fluorine analysis. The testing results are shown in Table 5.
TABLE 5______________________________________Surfactantused with Amount of fluorine on carpetfluoro- before after %Ex. chemical dyeing, dyeing, reten-No. Code % ppm ppm tion OR WR WOS______________________________________25 A,B 13,2 390 302 77 5 5 +1/226 -- -- 0 0 -- 0 NWR______________________________________
The test data show that the fluorochemical biuret provided the carpet with good oil and water repellency and useful soil resistance and was retained on the fiber through the drawing, texturing, tufting and dyeing processes.
In examples 27 and 28, two different rainwear fabrics were treated with an aqueous emulsion of a fluorochemical biuret of composition No. 2 of Table 2, in combination with a fluorochemical oxyalkylene and hydrocarbon nonionic surfactant, as indicated in Table 6. The fabrics were treated in a padding operation, dried at 150� C. for 10 min., and evaluated, together with untreated fabrics, examples 29 and 30, for initial oil repellency (OR) and resistance to a water spray (SR), then these properties evaluated again after 5 launderings (5L) and also after one dry cleaning (DC).
The OR test used was the above-described AATCC Standard Test 118-1978, the contact time before observation being the specified 30 sec., an OR value of 3 or greater being particularly desirable for rainwear fabrics.
The water spray rating (SR) is measured by AATCC Test Method 22-1979. The spray rating is measured using a 0 to 100 scale where 100 is the highest possible rating. In general, a spray rating of 70 or greater is desirable, particularly for outerwear fabrics.
The treated fabrics were laundered using a mechanically agitated automatic washing machine capable of containing a 4 kg load, using water at 50� C. and a commercial detergent, and then the washed fabrics were tunble-dried in an automatic dryer for 40 minutes at 70� C. and pressed in a flat-bed press (at 154� C.) before testing.
The treated fabrics were dry cleaned using perchloroethylene containing 1% of a dry cleaning detergent and tumbling in a motor driven tumble jar (AATCC Test Method 70-1975) for 20 minutes at 25� C. After removing excess solvent in a wringer, samples were dried at 70� C. for 10 minutes, then pressed on each side for 15 seconds on a flat-bed press maintained at 154� C.
The test data are summarized in Table 6.
TABLE 6______________________________________Surfactantused withfluoro-Ex. chemical % Fab- Initial 5L DCNo. Code % SOFa ricb OR SR OR SR OR SR______________________________________27 A,B 13,2 0.2 A 3 80 1 50 1 5028 A,B 13,2 0.2 B 5.5 70 2 50 1 7029 -- -- 0 A 0 0 0 0 0 030 -- -- 0 B 0 0 0 0 0 0______________________________________ a Percent fluorochemical solids on fabric b Fabric A is 100% woven polyester; fabric B is 100% nylon taffeta
The test data show that the rainwear fabrics were provided with oil and water repellency by the fluorochemical biuret, although oil repellency decreased after laundering and dry cleaning.
In examples 31-33, water-leaf paper sheets were treated with an aqueous emulsion of a fluorochemical biuret of composition No. 2 of Table 2, in combination with a fluorochemical oxyalkylene and hydrocarbon nonionic surfactant, as indicated in Table 8.
The paper sheets were treated with various concentration of the fluorochemical emulsion compositions using a laboratory size press (yielding a 93% wet pickup) and the sheets dried in a photo sheet dryer at 150� C. and evaluated for oil and water repellency. A comparative untreated paper sheet was also evaluated for oil and water repellancy. The results are given in Table 8.
TABLE 8______________________________________Surfactant Amount ofused with Concentration fluoro-fluoro- of chemical Oil WaterEx. chemical fluorochemical on paper, repel- repel-No. Code % in bath, wt. % wt. % lencya lencyb______________________________________31 A,B 13,2 1.54 0.3 5 15532 A,B 13,2 2.56 0.5 5 12533 A,B 13,2 5.12 1.0 6 11834 -- -- -- -- 0 NWR______________________________________ a This was determined by the "Kit Test" described as TAPPI Useful Method 557; the higher the value the better the repellency. b This was determined by the "Cobb Test" described as TAPPIT441-OS-77; the lower the value, the better the water repellency.
The test results show that the paper was provided with oil and water repellency by the application of the fluorochemical biuret, with levels of repellency increasing with increased fluorochemical biuret application.
The various modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this invention and this invention should not be restricted to that set forth herin for illustrative purposes.
|Cited Patent
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|Minnesota Mining & Mfg
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|Du Pont
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|Apr 13, 1971
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|Jun 17, 1970
|Apr 17, 1973
|Minnesota Mining & Mfg
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|Jul 22, 1975
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|Nov 14, 1973
|Oct 28, 1975
|Minnesota Mining & Mfg
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|Sep 12, 1974
|Mar 22, 1977
|E. I. Du Pont De Nemours And Company
|Oil and water repellent polymer containing onium groups
|Mar 3, 1975
|May 17, 1977
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|Aug 7, 1975
|Jun 14, 1977
|E. I. Du Pont De Nemours And Company
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|May 9, 1977
|Mar 13, 1979
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|Jun 16, 1977
|Aug 21, 1979
|Daikin Kogyo Co., Ltd.
|2-Hydroxy-1,1,2,3,3-pentahydro-perfluoroalkyl derivatives, their production and use
|Mar 30, 1979
|Feb 26, 1980
|Allied Chemical Corporation
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|Jan 12, 1977
|Jul 29, 1980
|Minnesota Mining And Manufacturing Company
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|Apr 28, 1981
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|Oct 6, 1981
|Taiho Pharmaceutical Company Limited
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|Apr 20, 1982
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|Aug 30, 1983
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|Jan 17, 1984
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|Oct 16, 1984
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|Mar 12, 1985
|Asahi Glass Company Ltd.
|Stainproofing agent and process for its preparation
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|Banks, R. E., Ed. "Organofluorine Chemicals and Their Industrial Applications," Ellis Horwood, Ltd., West Sussex 226-230 (1979).
|Banks, R. E., Ed. Organofluorine Chemicals and Their Industrial Applications, Ellis Horwood, Ltd., West Sussex 226 230 (1979).
|Citing Patent
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|Aug 24, 1984
|Sep 18, 1990
|E. I. Du Pont De Nemours And Company
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|Jun 7, 1994
|Nov 14, 1995
|United States Surgical Corporation
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|Jan 2, 1996
|E. I. Du Pont De Nemours And Company
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|Oct 13, 1998
|Mosbach; Klaus
|Stabilizers, polymers, and emulsions useful for molecular imprinting technology
|Jul 5, 1996
|Sep 28, 1999
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|Supports useful for molecular imprinting technology
|Jun 19, 2000
|Nov 12, 2002
|E. I. Du Pont De Nemours And Company
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|Oct 16, 2002
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|Milliken & Company
|Method of producing textile substrates having improved durable water repellency and soil release
|Jan 10, 2003
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|Jul 8, 2004
|Jan 2, 2007
|Scheidler Karl J
|Compositions for improving the light-fade resistance and soil repellancy of textiles and leathers
|Jun 3, 2005
|Aug 5, 2008
|Milliken & Company
|Textile substrates having layered finish structure for improving liquid repellency and stain release
|Jan 10, 2003
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|Milliken & Company
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|Jun 3, 2005
|Feb 3, 2009
|Yunzhang Wang
|Method for making textile substrates having layered finish structure for improving liquid repellency and stain release
|Dec 4, 2006
|Nov 2, 2010
|Scheidler Karl J
|Methods and compositions for improving light-fade resistance and soil repellency of textiles and leathers
|Oct 16, 2002
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|Kimbrell William C.
|Textile substrates having improved durable water repellency and soil release and method for producing same
|Jan 10, 2003
|Jul 15, 2004
|Kimbrell Wiliam C.
|Methods for imparting reversibly adaptable surface energy properties to target surfaces
|Jan 10, 2003
|Jul 15, 2004
|Kimbrell Wiliam C.
|Wash-durable, liquid repellent, and stain releasing polyester fabric substrates
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|Guerrero Cesar H
|Liquid resistant articles and method of producing the same
|Jun 3, 2005
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|Yunzhang Wang
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|Jun 3, 2005
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|U.S. Classification
|560/158, 442/89, 442/82, 252/8.62, 528/70, 442/80, 427/393.4, 442/92
|International Classification
|Cooperative Classification
|European Classification
|Dec 26, 1989
|Certificate of correction
|Sep 12, 1991
|Fee payment
Year of fee payment: 4
|Sep 27, 1995
|Fee payment
Year of fee payment: 8
|Sep 30, 1999
|Fee payment
Year of fee payment: 12


text:
Our tests are throwing an exception on social_panel.html accessing mozSocial. This is caused when our tests remove the test provider prior to the panel finishing it's load. The test code is setting a status panel during social.initialize, but none of the tests are verifying it is ready or shutdown, except the one test that uses it.
On occasion, it is also showing up during try runs for unrelated social patches.
Created attachment 658974 [details] [diff] [review]
test fixes
also fixes an https error in local testing when accessing example1.com
Comment on attachment 658974 [details] [diff] [review]
test fixes
[Approval Request Comment]
fixes tests in aurora

subset: commoncrawl


text:
- 1[only before noun] connected with magic powers and things that cannot be explained by reason or science synonym supernatural occult practices
- 2the occult noun [singular] everything connected with occult practices, etc. He's interested in witchcraft and the occult. Word Origin late 15th cent. (as a verb): from Latin occultare
BrE BrE//əˈkʌlt//, also BrE//ˈɒkʌlt//; NAmE NAmE//əˈkʌlt//
Check pronunciation: occult


text:
on 10/13/03 8:47 AM, Chris wrote:
> Of course I still
> teach, sing in a chorus, work on the executive board of my daylily club,
> run fund raisers, write, take care of my personal zoo, clean, cook,
> wash, shop, and sometimes even garden!
Chris -- Do you sleep LOL
Tony Veca <><
Another Gr888 Day in Paradise !!!!!
Vancouver, WA USA
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The Nike Lebron 12 was designed based on the scientific research and analysis of athletic performance done in the Nike Sports Research Lab. It is meant to enhance Lebrons explosiveness while providing him "superior cushioning, harnessed support, and natural flexibility". "Superior Cushioning" is achieved by the new hexagonally shaped Zoom Air bags on the sole which take the classic Zoom Air bag and divides it up to target specific pressure points on the foot. Using a combination of Dynamic Flywire and Hyperposite the shoe provides Lebron with "Harnessed Support" by locking down his foot and allowing him to be strong, fast and explosive. The new MegaFuse upper serves as a second outer skin that decreases weight, offers breathability and comfort, while giving the shoe it's "Natural Flexibility". This Lebron model is the embodiment of Nike's goal to continue innovating their designs by analyzing performance data and improving technology. This is the newest Lebron model so be sure to acquire this pair to continue your Nike Lebron collection.
Shipping Date: October 30th, 2014


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Generally don't like garden mums - the color palette is not to my
taste, combined with entirely too many petals. I like this one as I
can see the 'eye'. (I like the "florist mums", but am unwilling to do
the work required to have them in my garden!
Cathy, west central IL, z5b
On Oct 26, 2005, at 6:20 PM, Chris Petersen wrote:
> Today has finally dried out after New Yorks latest rainfall- a
> noreaster!
> I really felt like fall had begun as the temperature dropped into
> the 40s
> this morning and the trees started to show some of their fall
> colors. The
> mums are in their glory and I have so much C. 'Hillside Pink
> Sheffield' that
> I could decorate a hall with it. It has a wonderful aroma, but you
> dont
> want to be in a closed space with a vase of it!
> http://pg.photos.yahoo.com/ph/chrispnpt/detail?.dir=/
> 91c0&.dnm=4846.jpg
> Christine Petersen Northport, Long Island, New York
> Zone 7a (Average min temp 50 - 00)
> ---------------------------------------------------------------------
> To sign-off this list, send email to firstname.lastname@example.com with the
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text: Here's How To Sneak Into Candlestick ParkTom Ley8/01/14 2:01pmFiled to: candlestick parksan francisco 49ersnflfootball7018EditPromoteShare to KinjaToggle Conversation toolsGo to permalink That guy in the picture above is a reader who just emailed to tell us all about how he snuck into Candlestick Park yesterday, where he hung out on the field for about a half hour without anybody noticing or caring. The key to sneaking in appears to be wearing a suit and telling security you are there for an important meeting. Advertisement Take it away, brave reader:Well, I dragged my girlfriend over to the "stick" yesterday because I wanted to get one last look at the old girl before they tore her down. We pulled up to the parking lot and there was a dad in an SUV with his wife and kids in front of us trying to convince the security guard to let them in to take a picture of the stadium. The security guard was very adamant about not letting anyone in and instantly sent that family packing. I wasn't going to be denied. I confidently pulled up in my prius and tie (I had just came from a big time interview at the post office ) and told the security guard I had a meeting with mr. York and he waved me right in. Once we were in the parking lot I checked a few gates and they were all locked. My girlfriend was getting nervous and wanted to leave but, I wanted more.We drove around and found an open gate with some construction worked doing some construction and I saw my entrance!We marched right in and headed straight for the field. No one seemed to care/ notice we were in the stadium. I was in heaven ! I am a huge niner fan and I have been to countless games here. We hung out for about 30 minutes and we left after I tried to convince my girlfriend to head to the locker rooms. While in the stadium I was looking for something to take but, anything of value was bolted down or already gone. I did see a few lockers and a tanning bed randomly sitting about. I am sure alex smiths pale butt once laid in that bed. Actually if that tanning bed could talk that would be great. Maybe it was brought in for one specific player or who knows. Anyway we were inside for about a half hour or so and no one seemed to care we were there.One day, someone will finally be able to explain why sneaking into a stadium is a top-five fantasy for every American male. Reply70 repliesLeave a reply


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Coming in as part of a pack sharing the same similar "White Ice" theme, these Dunk High Premiums are the first of the lot to release from Nike Sportswear. The aesthetic is simple yet works extremely well together with a textured patent leather upper with an icy blue outsole. The translucent nature of the outsole reveals an asymmetric concentric circle pattern as well. Available now at Titolo.
Source: Nice Kicks


text:
Jesse: What a great thing...Robert is very sweet!
Melody, IA (Z 5/4)
"The most beautiful thing we can experience is the mysterious."
--Albert Einstein
--- On Thu 05/20, Jesse Bell < email@example.com > wrote:
From: Jesse Bell [mailto: firstname.lastname@example.com]
To: email@example.com
Date: Thu, 20 May 2004 14:07:03 -0700 (PDT)
Subject: [CHAT] Tiller!
My DH bought me a tiller! It's small enough for ME to handle, but
tough
enough and big enough to get the job done. I'm so jazzed. Last
night..I
set out to till one garden...and before I knew it...I had
about five
done. And I'm ready to till the world now. WOO HOO. I can
get so much
done in a short amount of time! Before, I was digging
beds by hand and
it took forever!!

Happy dance going on
in Oklahoma.

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text:
Mothers love their children no matter what.
Dead tired, they still forgive her mischievous all their endless pranks. Still, the children have to be assistants, so sooner or later, but to accustom children to work can not be avoided.
The point is not easy, and you do not just have a desire to give up all attempts of labor education.
Do not be tempted to do everything itself, you give your child time to acquire useful skills.
Especially because in the house there is always a simple operation, which under the force of the kids.
For example, to entrust your child to fill the bed is quite possible. Suppose that initially it will not quite turn out the way it should. The main thing here - this is the practice.
Expanding your things in the closet can also becharge of the child. Show how well it should be done. You can attach to each box stickers depicting the thing that should be there. Gradually pipsqueak learn to maintain order in their lockers.
The most simple task for the baby - is to remove their toys. Turn this thing in the game, and you do not run with the children's whims, but in the room the baby will always be in order.
Watering the flowers, too, are quite capable of kids. Fiddle with the water loves every child, but keep in mind that will be poured not only flowers, but also the furniture and the floor. Therefore, for safety, choose two or three flowers, put them in a place not fearful of water and follow the work of the crumbs. As soon as he begins to deal with the job, trust watering other plants in the apartment.
Caring for fish and other small householdanimals is also not difficult, moreover, instill your child kindness and attentiveness to others' needs. If there is a dog, the child's contact with it depends on many factors. Its rocks, nature, etc.
The most beloved children's game - it is serving and cleaning the table. That they are willing to engage in endlessly. Watch out for the safety of the child. Do not allow him to carry more than one device at a time.


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My father is 68 years old, and healthy. A house site measuring 60 feet x 40 feet in B.T.M. Layout is standing in his name which is his self acquired property. I am the only son for my parents. When I approached my Bank for grant of housing loan for construction over this site, they told me that since the property does not stand in my name either I have to get the property transferred in my name or I should hold this property jointly along with my father. Whether my father can Gift that property in my favour?
Your father can gift this site to you or deal with this site at his sweet will since this is his self acquired property. The stamp duty payable for the gift deed in Karnataka is Rs. 1000/-.


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- 1 [intransitive, transitive] to have the same opinion as somebody; to say that you have the same opinion When he said that, I had to agree. + speech 'That's true', she agreed. agree (with somebody) (about/on something) He agreed with them about the need for change. agree with something I agree with her analysis of the situation. agree (that)… We agreed (that) the proposal was a good one. 'It's terrible.' 'I couldn't agree more!' (= I completely agree) opposite disagree Express YourselfAgreeingIn a discussion, people may say certain things which you want to support. (In addition, before you make a negative comment, you may want to say first that there are points that you agree with.) Yes, that's true. That's right. On the other hand, there are some drawbacks to the plan… Exactly. Absolutely. Definitely. Yes, I suppose/guess so. I agree. It's definitely the best idea. I think you're right. We should listen to what they have to say. Sue is absolutely right. It's too early to make a decision now. I would go along with the idea that we should change the logo. We are in agreement on the best way to proceed, but we need to discuss the timing. (formal)
- 2 [transitive] if people are agreed or something is agreed, everyone has the same opinion about something be agreed (on/about something) Are we all agreed on this? be agreed (that…) It was agreed (that) we should hold another meeting. say yes
- 3 [intransitive, transitive] to say 'yes'; to say that you will do what somebody wants or that you will allow something to happen I asked for a pay rise and she agreed. agree to something Do you think he'll agree to their proposal? agree (that)… She agreed (that) I could go early. agree to do something She agreed to let me go early. Synonymsagreeaccept approve go along with somebody/something consentThese words all mean to say that you will do what somebody wants or that you will allow something to happen.agree to say that you will do what somebody wants or that you will allow something to happen:He agreed to let me go early.accept to be satisfied with something that has been done, decided or suggested:They accepted the court's decision.approve to officially agree to a plan, suggestion or request:The committee unanimously approved the plan.go along with somebody/something (rather informal) to agree to something that somebody else has decided; to agree with somebody else's ideas:She just goes along with everything he suggests.consent (rather formal) to agree to something or give your permission for something:She finally consented to answer our questions.Patterns to agree/consent to something to agree/consent to do something to agree to/accept/approve/go along with/consent to a plan/proposal to agree to/accept/approve a request decide
- 4 [intransitive, transitive] to decide with somebody else to do something or to have something agree on something Can we agree on a date? agree something They met at the agreed time. Can we agree a price? They left at ten, as agreed. agree to do something We agreed to meet on Thursday. agree what, where, etc… We couldn't agree what to do. More Like This Verbs usually followed by infinitives afford, agree, appear, arrange, attempt, beg, choose, consent, decide, expect, fail, happen, hesitate, hope, intend, learn, manage, mean, neglect, offer, prepare, pretend, promise, refuse, swear, try, want, wishSee worksheet. accept
- 5[transitive] agree something to officially accept a plan, request, etc. synonym approve Next year's budget has been agreed. be the same
- 6[intransitive] to be the same as something synonym tally The figures do not agree. agree with something Your account of the accident does not agree with hers. opposite disagree grammar
- 7[intransitive] agree (with something) to match a word or phrase in number, gender or person. In 'Tom likes jazz', the singular verb 'likes' agrees with the subject 'Tom'. See related entries: Grammar Word Origin late Middle English: from Old French agreer, based on Latin ad-
share opinion
verbjump to other results
BrE BrE//əˈɡriː//; NAmE NAmE//əˈɡriː//Verb Forms present simple I / you / we / they agree
BrE BrE//əˈɡriː//; NAmE NAmE//əˈɡriː//he / she / it agrees
BrE BrE//əˈɡriːz//; NAmE NAmE//əˈɡriːz//past simple agreed
BrE BrE//əˈɡriːd//; NAmE NAmE//əˈɡriːd//past participle agreed
BrE BrE//əˈɡriːd//; NAmE NAmE//əˈɡriːd//-ing form agreeing
BrE BrE//əˈɡriːɪŋ//; NAmE NAmE//əˈɡriːɪŋ//Grammar
if two people agree to differ, they accept that they have different opinions about something, but they decide not to discuss it any longer We must just agree to differ on this. Phrasal Verbsnot agree with somebody
agree to differjump to other results
Check pronunciation: agree


text:
More Videos...
Electric Drag Bike - 0 to 60 in Under 1 second
Neck breaking speed from an Electric Drag Bike.
GSX-R 1000 Blows By Cop Going About 160mph.
It's hard to see but this guy's at about 160+ mph when he passes a cop on his left (It's really quick). Does he stop? HELL NO, he ain't gonna stop just mashes the gas even more! THESE ARE NOT kmh.
Motorcycle Stunters VS. Cops Compilation - FNF
Watch from adrenaline rushing perspectives as these crazy and talented motorcycle stunters challenge authority and escape from police! Will they all escape? Spoiler: NO! Check out our facebook: http://www.facebook.com/failsandfightsonline Check out our twitter: http://www.twitter.com/failsandfights Check out our other channels: http://www.youtube.com/user/PoliceCompilations http://www.youtube.com/user/craziestviralvideos Credits: #1: https://www.youtube.com/watch?v=r9za7KDiSQo #2: https://www.youtube.com/watch?v=7qCRwDcDHCw #3: https://www.youtube.com/watch?v=Fd6syCGDPKU #4: https://www.youtube.com/watch?v=zqWTxIPK9cQ #5: https://www.youtube.com/watch?v=ktCTxO94kcY #6: https://www.youtube.com/watch?v=ZbpulwbeQ5I #7: https://www.youtube.com/watch?v=cLaoBVVDFmg All clips were either licensed for use, used with permission, or used and credited via U.S. Fair Use Copyright laws. Thank you for watching! THESE ACTIONS PRESENTED IN THESE VIDEOS ARE ILLEGAL AND DANGEROUS. We suggest you do not attempt to recreate these videos. Every video clip in this compilation was filmed on a closed course in Mexico with professional drivers as part of a police training initiative.
Vintage Electric Bicycles - Jay Leno's Garage
Andrew Davidge started his electric bike company in high school and now, four years later, he and Jay are cruising the Cruz and E-Tracker - at 36 mph in race mode with a 30-mile range! » Subscribe: http://bit.ly/JLGSubscribe » Visit the Official Site: http://bit.ly/JLGOfficialSite THE BEST OF JAY LENO'S GARAGE » Exclusive First Looks: http://bit.ly/JLGExclusives » Ultra Rare Supercars: http://bit.ly/JLGSupercars » Jay's Book Club: http://bit.ly/JLGBookClub JAY LENO'S GARAGE ON SOCIAL Facebook: http://facebook.com/JayLenosGarage Twitter: http://twitter.com/LenosGarage Instagram: http://instagram.com/jaylenosgarage/ ABOUT JAY LENO'S GARAGE A new video every Sunday! Visit Jay Leno's Garage, the Emmy-winning series where Jay Leno gives car reviews, motorcycle reviews, compares cars, and shares his passion and expertise on anything that rolls, explodes, and makes noise. Classic cars, restomods, super cars like the McLaren P1, sports cars like Porsche 918 Spyder and Camaro Z28, cafe racers, vintage cars, and much, much more. NBC ON SOCIAL: Full Episodes: http://NBC.com/video/library/full-episodes/ NBC YouTube: http://www.youtube.com/nbc Follow NBC: http://Twitter.com/NBC Like NBC: http://Facebook.com/NBC NBC Tumblr: http://NBCtv.tumblr.com/ NBC Pinterest: http://Pinterest.com/NBCtv/ NBC Google+: https://plus.google.com/+NBC NBC Instagram: http://instagram.com/nbctv Vintage Electric Bicycles - Jay Leno's Garage https://youtu.be/RCPy0d2KRSc Jay Leno's Garage http://www.youtube.com/user/jaylenosgarage


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Why more Israelis are shying away from interaction with Palestinians - Al-Monitor: the ... - 1 views
The Peace Index for March 2016, published by the Israel Democracy Institute, shows that a sizable majority of the Jewish public rejects the distinction between global terrorism, nurtured by radical Islam, and Palestinian terrorism, nurtured by the desire to shake off the Israeli occupation. Of those polled, 64% said they agree with the idea espoused by Prime Minister Benjamin Netanyahu that global terrorism and Palestinian terrorism are one and the same.
Israelis are in no rush to change the status quo
Some 78% think Israel should not take into consideration international demands to refrain from "targeted killings" (as the Israel Defense Forces calls the killing of wanted Palestinians), demolitions of family homes of Palestinians involved in attacks on Israelis and other questionable means used by the Israeli defense establishment in the fight against terrorism.
- ...4 more annotations...
the younger a person's age, the greater his or her resistance to a diplomatic process to end the conflict with the Palestinians. Those younger than 34 tend, more than older adults, to rule out compromise on core issues
The belief in Israeli society that there is no Palestinian partner for peace has taken hold and refuses to let go.
On the Israeli side, there is no entity like the one established by the Palestine Liberation Organization to maintain interaction with Israeli society. Abbas appointed his close associate Mohammed al-Madani to head this committee. In a conversation with Al-Monitor in fluent Hebrew, the deputy head of the committee, Elias Zananiri, said that he has no beef with the Israeli public running away from contact with the Palestinians.
"Of course I'm frustrated with our lack of success in breaching the walls of Israeli fear and loathing, but I'm not completely surprised," said Zananiri. "What do you expect of Jewish citizens whose leader questions the basic democratic rights of Israel's Arab citizens?"
Ed Webb on 09 Apr 16Ugh - don't read the comments


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Activator technique
|This article needs additional citations for verification. (December 2007) (Learn how and when to remove this template message)
The Activator Method Chiropractic Technique is a chiropractic treatment method and device created by Arlan Fuhr as an alternative to manual manipulation of the spine or extremity joints. The device is categorized as a mechanical force manual assisted (MFMA) instrument which is generally regarded as a softer chiropractic treatment technique.
Physical characteristics of the activator device[edit]
The activator is a small handheld spring-loaded instrument which delivers a small impulse to the spine. It was found to give off no more than 0.3 J of kinetic energy in a 3-millisecond pulse. The aim is to produce enough force to move the vertebrae but not enough to cause injury.[1]
Activator method chiropractic technique[edit]
The Activator Method Chiropractic Technique (AMCT) involves having the patient lie in a prone position and comparing the functional leg lengths. Often one leg will seem to be shorter than the other. The chiropractor then carries out a series of muscle tests such as having the patient move their arms in a certain position in order to activate the muscles attached to specific vertebrae. If the leg lengths are not the same, that is taken as a sign that the problem is located at that vertebra. The chiropractor treats problems found in this way moving progressively along the spine in the direction from the feet towards the head.[1]
Leg length test reliability[edit]
Although prone "functional leg length" is a widely used chiropractic tool, it is not a recognized anthropometric technique, since legs are often naturally of unequal length, and measurements in the prone position are not entirely valid estimates of standing X-ray differences.[2] Measurements in the standing position are far more reliable.[3] Another confounding factor is that simply moving the two legs held together and leaning them imperceptibly to one side or the other produces different results.[4] Fuhr claims that properly trained doctors show good interexaminer reliability.[1]
Utilization rates[edit]
In 2003, the National Board of Chiropractic Examiners found that 69.9% of chiropractors used the technique, and 23.9% of patients received it.[5] The majority of US chiropractic schools and some schools in other countries teach the AMCT method, and an estimated 45,000 chiropractors worldwide use AMCT or some part of the technique.[1]
There have been a number of studies of AMCT, including case reports, clinical studies and randomized controlled trials, but there are still unanswered questions. A few studies suggest that the activator may be as effective as manual adjustment in treatment of back pain.[1]
See also[edit]
- ^ a b c d e Fuhr, Arlan W.; J. Michael Menke (February 2005). "Status of Activator Methods Chiropractic Technique, Theory, and Practice". Journal of Manipulative and Physiological Therapeutics. 28 (2): e1–e20. doi:10.1016/j.jmpt.2005.01.001. PMID 15800504. Retrieved 2008-08-18.
- ^ D W Rhodes, E R Mansfield, P A Bishop, J F Smith. The validity of the prone leg check as an estimate of standing leg length inequality measured by X-ray. J Manipulative Physiol Ther. ;18 (6):343-6
- ^ E Hanada, R L Kirby, M Mitchell, J M Swuste. Measuring leg-length discrepancy by the "iliac crest palpation and book correction" method: reliability and validity. Arch Phys Med Rehabil. 2001 Jul ;82 (7):938-42
- ^ Keeping Your Spine In Line, Adjusting the Joints, and Video, Alan Alda, PBS, Scientific American Frontiers. Video discusses Activator and leg length
- ^ Christensen MG, Kollasch MW (2005). "Professional functions and treatment procedures" (PDF). Job Analysis of Chiropractic. Greeley, CO: National Board of Chiropractic Examiners. pp. 121–38. ISBN 1-884457-05-3. Retrieved 2008-08-25.


text:
Hello, Donna! I'd love to see those cicada pictures. The number of KBs
might be a problem for my webmail, though. If any of them are over 200
KB, could you please either compress them (I hope that is the right
term--a computer genius I am not!) or send one picture per day?
I have a friend who is collecting cicadas for her son, the entymologist.
I'm under orders to nab the little sprats alive and give 'em to her, if
I can!
Thanks in advance,
Wendy in SW OH
-----Original Message-----
From: Donna <>
Sent: May 22, 2004 4:16 PM
To: firstname.lastname@example.com
Subject: [CHAT] cicada pictures
I am sure some of you are very familiar with the Cicada locust invasion.
For those not experiencing this 17 year old tradition a friend of mine
has pictures documented the emerging thru hatching process this morning
in Maryland. I inquired how long this took and he thought it was only a
few hours.
If anyone would like to see them, I can send them in 4 private emails to
you. He doesn't want his pictures on the net, but is fine with me
forwarding them to anyone... why doesn't this make sense to me?!?
I found his photo series very interesting. If anyone would like to see
them, let me know.
Where it is raining again......:(
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Sunset in Calgary By Tara C
Going West on the new Stoney Trail Rd. NW
Mar 30, 2011
Candid Captures
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Thrill Seekersview details
Thrill seekers warning: the activities listed above and similar activities are considered hazardous and extremely fun.
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What do ballet, tapas and fly fishing have in common? They're but three of the hidden surprises you'll find within Calgary's city limits.
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Review Hot and Cold: A 3D Hidden Object Adventure (DSiWare)
Will it light your fire or stink on ice?
Review A Little Bit of... Magic Made Fun: Psychic Camera (DSiWare)
It doesn't take a psychic to figure out this isn't worth your time.
Review Littlest Pet Shop (DSiWare)
With seven different DS releases to choose from, was this really necessary?


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Preheat oven to 350 degrees.
In large bowl, toss together nuts, syrup, oil and all of the spices except salt and pepper.
Spread on foil-lined baking sheet and bake in preheated oven 15 minutes, stirring occasionally, until browned. Season to taste with salt and pepper. Toss frequently until cooled.
Read and share your thoughts on this story.


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Aftermath may be all men, but they travel a long way away from dudeprov. Starting with a pair of stories from the audience, each scene in their set feeds the next until they build an entire world. Or they collapse in exhaustion. Whichever comes first.Tuesday @ 7:30 PM
Change Machine is an Arcade Comedy Theater house team that has been learning and growing together for over two years. Their show begins with a small, honest moment and takes you through a labyrinth of thematically connected twists and turns in which anything can happen.Saturday @ 7:00 PM
Charmsical gives the audience the musical it has always wanted to see. You give us the title and we take it from there.Thursday @ 7:30 PM
Formed in 1992, the Comedy Pigs have performed at national comedy festivals, been featured on Comedy Central, and have been guests at the National Pork Producers Convention. The Comedy Pigs perform regularly at Maryland Ensemble Theatre in Frederick, MD.Wednesday @ 7:30 PM
In this improvised show ArtAlive!, Kate takes art history off its erudite shelf and give people a, visceral, emotional connection with an artist they love.Monday @ 7:30 PM
He's from Philly. She's from Washington, DC. They met at an improv festival in Harrisburg, PA, and now they are married. What are the odds? Girlfight! explores relationships (naturally!) using the montage. Performing since 2013 (and married since 2014), Girlfight! presents the unique opportunity for two people who share their lives offstage to share their love and craft of improv on stage.Friday @ 7:00 PM
Goats has been seen at festivals all over the northeast. From Del Close Marathon, Boston Comedy Arts Festival to closing out the New York Musical Improv Festival, Goats has brought a fun physical brand of musical improv and inspired people to want to do musical improv. Nothing is unused, from props to chairs. Goats also has the found the fun of combining regular improv effects like tags, beats, time dashes to be able to provide a fuller musical improv show. Eitan Levine is the co-host of "Who Won The Internet", Catherine Wing and Steve Whyte are formerly of the long running musical improv team "Bees!!", and Justin D. Torres provides Voice over work for hundreds of websites per year.Sunday @ 7:00 PM
Gus performs a fast-paced, ridiculous style of improv comedy. They've performed at festivals all over the U.S., and they've performed with everyone from burlesque girls to modern dancers, and even their parents. They are easily excited.Wednesday @ 7:30 PM
We've been here for a while. Fun and smart and sometimes a little blue. We like when people have fun.Sunday @ 7:00 PM
Heartbeat is a Magnet House Team specializing in the Spokane. Based in a firm grounded monoscene, Heartbeat heightens the world surrounding the location to the point where the world changes the monoscene itself. Made up of seasoned Magnet Theater graduates, Heartbeat performs weekly at the Magnet theater on Wednesday nights.Friday @ 10:00 PM
Inspired by the popular series Drunk History, a group of sober improvisers try to keep up with an extremely drunk narrator in "History Under the Influence." Kevin spends the hour before the show getting hammered, then stumbles onstage and asks the audience for a historical event they'd like to see re-enacted. The result is wacky, hilarious, and occasionally accurate. Since 2014, History Under the Influence has performed at improv festivals in five different states and four different countries, most recently IMPRO Amsterdam!Saturday @ 7:00 PM
Honey is a group of three or four friends that takes inspiration from each other on and off stage. Our long form presentation is an exercise in love and silliness, two things we love to see more of on stage. Honey was an official selection of the several festivals in large cities over the past 5 years. They are one of the most well-traveled NYC improv teams.Saturday @ 10:00 PM
Grab your passport and kiss your mommy and daddy goodbye, Hostel is open for business, and they love to play with others! This group of global improv citizens welcome improvisers from all over to play in for each of their shows, sharing the best of BIG's Charm City stage with some of the funniest folks across the map.Wednesday @ 7:30 PM
Like a comedy version of The Babysitters Club, HOTLINE is an all-lady Philadelphia improv troupe that incorporates music and dance into their sets. The choreographer of Dirty Dancing has described HOTLINE as a "collective force of kindred spirits that share a strong yet gentle affection for one another." They perform regularly around Philadelphia and are directed by the Philly Improv Theater's improv director, Kristen Schier.Saturday @ 10:00 PM
Impromptune is a group of experimental improvisers and musicians working together to explore the use of song as a medium for improv. The troupe is working toward performing full-length improvised musicals.Thursday @ 7:30 PM
Babs (Christina Enoch Kemmerer) and Midge (Bridget Cavaiola) have been singing cabaret hits together since they were young ladies just learning how to keep down their chardonnay. They love fur wraps, sequins, their lovers, and of course their faithful and handsome piano man, Sam (Jeff Waters). These ladies will improvise all of your favorite hits and make you feel all warm inside. And outside.Sunday @ 7:00 PM
A cast of singer-improvisers instantly creates a compelling new show with each performance, comprised of completely improvised scenes, lyrics and music, all inspired by a single audience suggestion. The Washington Post calls iMusical "spot on." The cast has performed to standing ovations in multiple comedy festivals including ones in Baltimore, Philadelphia, and New York as well as at venues across the DC area including the Kennedy Center. Under the direction of Travis Charles Ploeger, former longtime member of New York's renowned Chicago City Limits, iMusical explores the human condition via song and laughter … as only WIT can!Thursday @ 7:30 PM
Irony City is a close-knit crew of improvisers with backgrounds in comedy, theater, and writing who come together to tell believable stories on stage about odd characters in dramatic situations. Founded in 2006, the nearly 10 years of experience together results in a style of experimentation and playfulness in their monthly show at the Arcade Comedy Theater and in one-off creations such as the Irony City Holiday Reunion Spectacular!, An Improvised Musical Fairy Tale at the Pittsburgh Children's Museum, and Play It By Ear: An Improvised Play by Irony City. Official Selection: Phoenix Improv Festival (2015), Detroit Improv Festival (2015).Saturday @ 10:00 PM
We are the Resident Cast of the Pointless Brewery & Theatre in Ann Arbor, MI. We perform Long Form improv on Friday and Saturday nights as well as corporate events in SE Michigan.Friday @ 10:00 PM
Lekker has been a BIG mainstage troupe since 2009; not ones to rest on their laurels, Lekker constantly challenges themselves to try new formats and find new connections with their audiences. Their strength is in the emotions; their performances are mainly relationship-driven, and they strive to find human moments in the most ridiculous of situations.Tuesday @ 7:30 PM
Love Onion fills your nostrils with fragrant umami and makes your eyes well up with giggle-tears. Based on the audience suggestion, this Washington Improv Theater house ensemble creates a new format each show that explores that suggestion through the themes, structure, and editing that develops in the first couple scenes. It could stay in one room or explore the universe; it could be familiar or utterly bonkers; it could use some salt or be well-seasoned. Love Onion doesn't know where they're going, but they're damn excited to get there!Friday @ 7:00 PM
Man vs Movie (the world's only one-man improvised movie) is a one man show with a cast of thousands. Veteran improviser Paul Vaillancourt takes a single suggestion of a line of poetry or a lyric from a song and, using that as his jumping off point, improvises an entire feature film right before your very eyes including everything you would see in a big budget Hollywood movie - camera angles, plot, characters, special effects and more.Saturday @ 8:30 PM
Minority Re'port is a unique troupe representing the underrepresented in improv. With our mix of high-energy, audience-inspired improv, we create characters you'll never forget, and leave you as satisfied as your mama's sweet potato pie.Monday @ 7:30 PM
Plan B is the longest running troupe in BIG's comedy arsenal. Expect short form (Whose Line is it Anyway?-style) games with high energy, big characters, and major laughs!Tuesday @ 7:30 PM
By day, we push paper; by night, we press play. Improv from the funniest in Washington, DC.Monday @ 7:30 PM
Prettier Than You, is, um, prettier than you. Together since 2011, Prettier Than You has performed at the Chicago Improv Festival, Charm City Comedy Festival, Comedy Pigs Festival (Frederick, MD), Washington Improv Theater, and the Unified Scene Theater (Washington, DC).Friday @ 10:00 PM
A diverse group of Baltimore Improvisers, Remote Possibilities combine their two loves (episodic television and long form improv) to present a brand new episode in a long running series that heretofore has never existed. Whether it is a teen drama, police procedural, super hero saga, or sci-fi adventure, you are sure to be on a ride you'll never forget.Tuesday @ 7:30 PM
This Harold team is BIG's newest Main Stage troupe!Monday @ 7:30 PM
Sad Trombone is the comedy duo of improv veterans Ralph Andracchio and Steve Kleinedler. Give us your disappointments, and we'll give you a funny show. With no regrets.Wednesday @ 7:30 PM
Sistine Robot is one of the Washington, D.C. area's longest-running independent long-form improv teams. The Robots have taken the stage at Washington Improv Theater, the Baltimore Improv Festival, the District Improv Festival, the Providence Improv Fest and Maryland Ensemble Theater. They host the venerable monthly show "Enjoy an Appletini with Sistine Robot" in the basement of a local gay bar. With a style that is both smart and silly, Sistine Robot is proof that robots CAN learn to love.Friday @ 8:30 PM
Swartzlander hails from New York City, where they've performed at UCB, The Magnet, and possibly millions of other venues. Performing together for over eight years has given them a deep knowledge of each other's darkest secrets, and they are more than willing to exploit those on stage, for your benefit! Join them for what is guaranteed to be a weird, fantastic journey.Saturday @ 8:30 PM
Follow around the cast and crew of a [one-night-only / improvised-just-for-you / that's-right-entirely-made-up] play, as they move from on-stage to off, and in and out of "character." Will the theatrical star-crossed lovers be secret off-stage enemies? Will the stage manager die halfway through the production, leaving the cast cue-less and clue-less? Will the entire original cast get horrible food poisoning so that the play must be performed entirely by understudies? All of this - AND MORE - might happen! Come for the fake play. Stay for the fake players.Friday @ 8:30 PM
A never before seen collection of teachers from BIG and visiting troupes.Saturday @ 7:00 PM
Training for Prom performs longform improv that's at once familiar and bizarre. This puckish troupe combines whimsy with emotional connection to bring you along for a ride that flips reality through the looking glass. They have performed in the Charm City Fringe Festival and the New York City Improv Festival, as well as the Baltimore Improv Festival.Friday @ 7:00 PM