The present invention relates to laundry detergent compositions providing dye protection benefits to fabric comprising: a) from about 4% to about 70% by weight, of a surfactant; b) from about 0.01% by weight, of a dye maintenance polymer or oligomer, said polymer or copolymer comprising one or more linearly polymerizing monomers, cyclically polymerizing monomers, and mixtures thereof; and c) the balance carriers and adjunct ingredients.

The present invention relates to compositions, in either liquid or granular form, for use in laundry applications, wherein the compositions comprise certain dye maintenance polymers that have a net positive charge. Compositions comprising the dye maintenance polymers of this invention impart appearance and integrity benefits to fabrics and textiles laundered in washing solutions formed from such compositions.
It is, of course, well known that alternating cycles of using and laundering fabrics and textiles, such as articles of worn clothing and apparel, will inevitably adversely affect the appearance and integrity of the fabric and textile items so used and laundered. Fabrics and textiles simply wear out over time and with use. Laundering of fabrics and textiles is necessary to remove soils and stains which accumulate therein and thereon during ordinary use. However, the laundering operation itself, over many cycles, can accentuate and contribute to the deterioration of the integrity and the appearance of such fabrics and textiles.
Deterioration of fabric integrity and appearance can manifest itself in several ways. Short fibers are dislodged from woven and knit fabric/textile structures by the mechanical action of laundering. These dislodged fibers may form lint, fuzz or xe2x80x9cpillsxe2x80x9d which are visible on the surface of fabrics and diminish the appearance of newness of the fabric. Further, repeated laundering of fabrics and textiles, especially with bleach-containing laundry products, can remove dye from fabrics and textiles and impart a faded, worn out appearance as a result of diminished color intensity, and in many cases, as a result of changes in hues or shades of color.
Given the foregoing, there is clearly an ongoing need to identify materials which could be added to laundry products that would associate themselves with the fibers of the fabrics and textiles laundered using such products and thereby reduce or minimize the tendency of the laundered fabric/textiles to deteriorate in appearance. Any such detergent product additive material should, of course, be able to benefit fabric appearance and integrity without unduly interfering with the ability of the laundry product to perform its intended function. The present invention is directed to the use of dye maintenance polymers in laundry applications that perform in this desired manner.
The present invention meets the aforementioned need in that it has been surprisingly discovered that fabric which is treated, and subsequently re-treated with the compositions of the present invention, will resist normal fading and color loss without regard to the circumstances, inter alia, due to mechanical wear and abrasion. In addition, fabric which has not been treated can have the loss of fabric dye attenuated by washing clothing with the laundry detergent compositions of the present invention. The compositions of the present invention can take any form, inter alia, heavy duty liquid (HDL), heavy duty granular (HDG), bars, pastes, thixotropic compositions.
The first aspect of the present invention relates to laundry detergent compositions providing dye protection benefits to fabric comprising:
a) from about 4% to about 70% by weight, of a surfactant selected from the group consisting of nonionic, anionic, cationic, amphoteric, zwitterionic surfactants and mixtures thereof, preferably at least one of said surfactants is an anionic surfactant;
b) from about 0.01%, preferably from about 0.1%, more preferably from about 0.5%, most preferably from about 0.8% to about 10%, preferably to about 8%, more preferably to about 6%, most preferably to about 5% by weight, of a dye maintenance polymer or oligomer, said polymer or copolymer comprising one or more units having the formula:
I) linear polymer units having the formula:
xe2x80x83wherein each R1 is independently
a) hydrogen;
b) C1-C4 alkyl;
c) substituted or unsubstituted phenyl;
d) substituted or unsubstituted benzyl;
e) carbocyclic;
f) heterocyclic;
g) and mixtures thereof;
each R2 is independently
a) hydrogen;
b) halogen
c) C1-C4 alkyl;
d) C1-C4 alkoxy;
e) substituted or unsubstituted phenyl;
f) substituted or unsubstituted benzyl;
g) carbocyclic;
h) heterocyclic;
i) and mixtures thereof;
each Z is independently
a) hydrogen;
b) hydroxyl;
c) halogen;
d) xe2x80x94(CH2)mR;
wherein R is:
i) hydrogen;
ii) hydroxyl
iii) halogen;
iv) nitrilo;
v) xe2x80x94OR3;
vi) xe2x80x94O(CH2)nN(R3)2;
vii) xe2x80x94O(CH2)nN+(R3)3Xxe2x88x92;
viii) xe2x80x94OCO(CH2)nN(R3)2;
ix) xe2x80x94OCO(CH2)nN+(R3)3Xxe2x88x92;
x) xe2x80x94NHCO(CH2)nN(R3)2;
xi) xe2x80x94NHCO(CH2)nN+(R3)3Xxe2x88x92;
xii) xe2x80x94(CH2)nN(R3)2;
xiii) xe2x80x94(CH2)nN+(R3)3Xxe2x88x92;
xiv) carbocyclic;
xv) heterocyclic;
xvi) nitrogen heterocycle quaternary ammonium;
xvii) nitrogen heterocycle N-oxide;
xviii) aromatic N-heterocyclic quaternary ammonium;
xix) aromatic N-heterocyclic N-oxide;
xx) xe2x80x94NHCHO;
xxi) or mixtures thereof;
each R3 is independently hydrogen, C1-C8 alkyl, C2-C8 hydroxyalkyl, and mixtures thereof; X is a water soluble anion; the index n is from 0 to 6
e) xe2x80x94(CH2)mCORxe2x80x2
wherein Rxe2x80x2 is
i) xe2x80x94OR3;
ii) xe2x80x94O(CH2)nN(R3)2;
iii) xe2x80x94O(CH2)nN+(R3)3Xxe2x88x92;
iv) xe2x80x94NR3(CH2)nN(R3)2;
v) xe2x80x94NR3(CH2)nN+(R3)3Xxe2x88x92;
vi) xe2x80x94(CH2)nN(R3)2;
vii) xe2x80x94(CH2)nN+(R3)3Xxe2x88x92;
viii) or mixtures thereof;
each R3 is independently hydrogen, C1-C8 alkyl, C2-C8 hydroxyalkyl, and mixtures thereof; X is a water soluble anion; the index n is from 0 to 6;
f) and mixtures thereof; the index m is from 0 to 6;
II) cyclic units derived from cyclically polymerizing monomers having the formula:
xe2x80x83wherein each R4 is independently an olefin comprising unit which is capable of propagating polymerization in addition to forming a cyclic residue with an adjacent R4 unit; R5 is C1-C12 linear or branched alkyl, benzyl, substituted benzyl, and mixtures thereof; X is a water soluble anion; and
III) mixtures thereof; provided said polymer or co-polymer has a net cationic charge; and wherein said dye maintenance polymer is not an polyethyleneimine or alkoxylated derivative thereof; and
b) the balance carriers and other adjunct ingredients.
In addition to the surfactant and the dye maintenance polymer of this invention, the laundry detergent compositions herein comprise from about 0.01% to 80% by weight of an organic or inorganic detergency builder and other conventional laundry detergent products. In its method aspect, the present invention relates to the laundering or treating of fabrics and textiles in aqueous washing, rinsing, or treating solutions formed from effective amounts of any of the detergent compositions, fabric softener compositions, or aqueous solution treatments described herein, or formed from the individual components of such compositions. Laundering of fabrics and textiles in such washing, rinsing and/or treatment solutions, followed by drying, imparts fabric appearance benefits to the fabric and textile articles so treated. Such benefits can include improved overall appearance, pill/fuzz reduction, anti-fading, improved abrasion resistance, and/or enhanced softness. It has been surprisingly determined that the dye maintenance polymers of this invention impart fabric appearance and integrity benefits that are greater than the benefits achieved by a corresponding amount of either component by itself.
These and other objects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (xc2x0C.) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.
As noted, when fabric or textiles are laundered in solutions which comprise the dye maintenance polymers of the present invention fabric appearance and integrity are enhanced. The dye maintenance polymers can be added to wash solutions by incorporating them into a detergent composition, a fabric softener or by adding them separately to the washing solution. The dye maintenance polymers are described herein primarily as liquid or granular detergent additives but the present invention is not meant to be so limited. The dye maintenance polymers, detergent composition components, optional ingredients for such compositions and methods of using such compositions, are described in detail below. All percentages are by weight unless other specified.
Dye Maintenance Polymers
Compositions and systems of the present invention comprise from about 0.1%, preferably for about 1%, more preferably from about 2%, most preferably from about 3% to about 10%, preferably to about 7%, more preferably to about 5% by weight, of a polymer, co-polymer, or mixture thereof, wherein said polymer or co-polymer comprises at least one cationically charged unit, inter alia, quaternary ammonium moiety or unit which can form a cationic charge in situ, inter alia, primary amine moiety. Stated in another way, the oligomer, polymer, or co-polymer resulting from the herein below described monomer units must have a net cationic charge. The charge can be distributed among any of the herein described units.
The dye maintenance polymers of this invention can be used in any fabric laundering process and provide certain appearance benefits to the fabrics laundered in these processes. Such fabric appearance benefits can include, for example, improved overall appearance of the laundered fabrics, reduction of the formation of pills and fuzz, protection against color fading, improved abrasion resistance, etc. The dye maintenance polymers used in the compositions and methods herein can provide such fabric appearance benefits when incorporated in a wash or rinse added products.
As will be apparent to those skilled in the art, an oligomer is a molecule consisting of only a few monomer units while polymers comprise considerably more monomer units. For the present invention, oligomers are defined as molecules having an average molecular weight below about 1,000 and polymers are molecules having an average molecular weight of greater than about 1,000. Copolymers are polymers or oligomers wherein two or more dissimilar monomers have been simultaneously or sequentially polymerized. Copolymers of the present invention can include, for example, polymers or oligomers copolymerizing acrylamide with dimethyldiallylammonium chloride, vinyl amine with vinyl alcohol, etc
Cationic polymers in general and their method of manufacture are know. For example, a detailed description of cationic polymers can be found in an article by M. Fred Hoover that was published in the Journal of Macromolecular Sciencexe2x80x94Chemistry, A4(6), pp 1327-1417, October, 1970. The entire disclosure of the Hoover article is incorporated herein by reference. The dye maintenance polymers of this invention will be better understood when read in light of the Hoover article, the present disclosure and the Examples herein.
I) Linear Polymer Units
The polymers or co-polymers of the present invention can comprise one or more linear polymer units having the formula:
wherein R1, R2, and Z are defined herein below. Preferably, the linear polymer units are formed from linearly polymerizing monomers. Linearly polymerizing monomers are defined herein as monomers which under standard polymerizing conditions result in a linear polymer chain or alternatively which linearly propagate polymerization. The linearly polymerizing monomers of the present invention have the formula:
however, those of skill in the art recognize that many useful linear monomer units are introduced indirectly, inter alia, vinyl amine units, vinyl alcohol units, and not by way of linearly polymerizing monomers. For example, vinyl acetate monomers once incorporated into the backbone are hydrolyzed to form vinyl alcohol units. For the purposes of the present invention, linear polymer units may be directly introduced, i.e. via linearly polymerizing units, or indirectly, i.e. via a precursor as in the case of vinyl alcohol cited herein above.
Each R1 is independently hydrogen, C1-C4 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocyclic, heterocyclic, and mixtures thereof. Preferably R1 is hydrogen, C1-C4 alkyl, phenyl, and mixtures thereof, more preferably hydrogen and methyl.
Each R2 is independently hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocyclic, heterocyclic, and mixtures thereof. Preferred R2 is hydrogen, C1-C4 alkyl, and mixtures thereof. Each Z is independently hydrogen; hydroxyl; halogen; xe2x80x94(CH2)mR, wherein R is hydrogen, hydroxyl, halogen, nitrilo, xe2x80x94OR3, xe2x80x94O(CH2)nN(R3)2, xe2x80x94O(CH2)nN+(R3)3Xxe2x88x92, xe2x80x94OCO(CH2)nN(R3)2, xe2x80x94OCO(CH2)nN+(R3)3Xxe2x88x92, xe2x80x94NHCO(CH2)nN(R3)2, xe2x80x94NHCO(CH2)nN+(R3)3Xxe2x88x92, xe2x80x94(CH2)nN(R3)2, xe2x80x94(CH2)nN+(R3)3Xxe2x88x92, a non-aromatic nitrogen heterocycle comprising a quaternary ammonium ion, a non-aromatic nitrogen heterocycle comprising an N-oxide moiety, an aromatic nitrogen containing heterocyclic wherein one or more or the nitrogen atoms is quaternized; an aromatic nitrogen containing heterocycle wherein at least one nitrogen is an N-oxide; xe2x80x94NHCHO (formamide), or mixtures thereof; wherein each R3 is independently hydrogen, C1-C8 alkyl, C2-C8 hydroxyalkyl, and mixtures thereof; X is a water soluble anion; the index n is from 0 to 6; carbocyclic, heterocyclic, or mixtures thereof; xe2x80x94(CH2)mCORxe2x80x2 wherein Rxe2x80x2 is xe2x80x94OR3, xe2x80x94O(CH2)nN(R3)2, xe2x80x94O(CH2)nN+(R3)3Xxe2x88x92, xe2x80x94NR3(CH2)nN(R3)2, xe2x80x94NR3(CH2)nN+(R3)3Xxe2x88x92, xe2x80x94(CH2)nN(R3)2, xe2x80x94(CH2)nN+(R3)3Xxe2x88x92, or mixtures thereof, wherein R3, X, and n are the same as defined herein above. A preferred Z is xe2x80x94O(CH2)nN+(R3)3Xxe2x88x92, wherein the index n is 2 to 4. The index m is from 0 to 6, preferably 0 to 2, more preferably 0.
Non-limiting examples of linearly polymerizing monomers comprising a heterocyclic Z unit includes 1-vinyl-2-pyrrolidinone, 1-vinylimidazole, 2-vinyl-1,3-dioxolane, 4-vinyl-1-cyclohexene1,2-epoxide, and 2-vinylpyridine.
The polymers and co-polymers of the present invention comprise Z units which have a cationic charge or which result in a unit which forms a cationic charge in situ. When the co-polymers of the present invention comprise more than one Z unit, for example, Z1, Z2, . . . Zn units, at least about 1% of the monomers which comprise the co-polymers will comprise a cationic unit. Preferred cationic units include xe2x80x94O(CH2)nN+(R3)3Xxe2x88x92 and xe2x80x94(CH2)nN+(R3)3Xxe2x88x92. When the co-polymers of the present invention are formed from two monomers, Z1 and Z2, the ratio of Z1 to Z2 is preferably from about 9:1 to about 1:9.
A non-limiting example of a Z unit which can be made to form a cationic charge in situ is the xe2x80x94NHCHO unit, formamide. The formulator can prepare a polymer or co-polymer comprising formamide units some of which are subsequently hydrolyzed to form vinyl amine equivalents. For example the formulator may prepare a co-polymer having the general formula:
which comprises a formamide unit and then subsequently treat the co-polymer such that some of the formamide units are hydrolyzed to form a co-polymer comprising vinyl amine units, said polymer having the formula:
wherein Z may be a cationic unit comprising or non-cationic unit comprising moiety and xxe2x80x2+xxe2x80x3=x.
Another class of preferred linearly polymerizable monomers comprise cationically charged heteroaromatic Z units having the formula:
an non-limiting example of which is 4-vinyl (N-alkyl)pyridine wherein R1 and R2 are each hydrogen and R6 is methyl.
Another class of preferred linearly polymerizable monomers which comprises a heterocyclic ring includes Z units comprising an N-oxide, for example, the N-oxide having the formula:
a non-limiting example of which is 4-vinyl pyridine N-oxide.
N-alkyl vinylpyridine monomers and N-oxide vinylpyridine monomers can be suitably combined with other non aromatic monomers, inter alia, vinyl amine. However, preferred polymers of the present invention include copolymers derived from a combination of quaternized, N-oxide, and nitrogen containing heteroaromatic monomers, non-limiting examples of which includes a copolymer of N-methyl vinyl pyridine and vinyl pyridine in a ratio of 4:1; a copolymer of N-methyl vinyl pyridine and vinyl pyridine in a ratio of 4:6; a co-polymer of poly(N-methyl vinyl pyridine) and vinyl pyridine N-oxide in a ratio of polymer to monomer of 4:1; poly(N-methyl vinyl pyridine) and vinyl pyridine N-oxide in a ratio of polymer to monomer of 4:6; and mixtures thereof.
A preferred linear co-polymer according to the present has the formula:
wherein Z1 has the formula:
Z2 has the formula:
wherein X is chlorine; x has the value of from about 10 to about 100,000; y has the value of from about 10 to about 100,000; the ratio of x to y is from 9:1 to 1:9. Co-polymers of this type are available as, e.g., Sedipur(copyright) CF104 ex BASF. As described herein above, some preferred polymer residues may be formed by treatment of the resulting polymer. For example, vinyl amine residues are preferably introduced via formamide monomers which are subsequently hydrolyzed to the free amino unit. Also vinyl alcohol units are obtained by hydrolysis of residues formed form vinyl acetate monomers. Likewise, acrylic acid residues may be esterified after polymerization, for example, units having the formula:
may be more conveniently formed after the backbone has been formed by polymerization with acrylic acid or acrylic acid precursor monomers.
II) Cyclic Units Derived from Cyclically Polymerizing Monomers
The polymers or co-polymers of the present invention can comprise one or more cyclic polymer units which are derived from cyclically polymerizing monomers. Cyclically polymerizing monomers are defined herein as monomers which under standard polymerizing conditions result in a cyclic polymer residue as well as serving to linearly propagate polymerization. Preferred cyclically polymerizing monomers of the present invention have the formula:
wherein each R4 is independently an olefin comprising unit which is capable of propagating polymerization in addition to forming a cyclic residue with an adjacent R4 unit; R5 is C1-C12 linear or branched alkyl, benzyl, substituted benzyl, and mixtures thereof; X is a water soluble anion.
Non-limiting examples of R4 units include allyl and alkyl substituted allyl units. Preferably the resulting cyclic residue is a six-member ring comprising a quaternary nitrogen atom.
R5 is preferably C1-C4 alkyl, preferably methyl.
An example of a cyclically polymerizing monomer is dimethyl diallyl ammonium having the formula:
which results in a polymer or co-polymer having units with the formula:
wherein preferably the index z is from about 10 to about 50,000.
III) Mixtures Thereof
The polymers or co-polymers of the present invention must retain a net cationic charge, whether the charged is developed in situ, or whether the polymer or co-polymer itself has a formal positive charge. Preferably the polymer or co-polymer has at least 10%, more preferably at least about 25%, more preferably at least about 35%, most preferably at least about 50% of the residues comprise a cationic charge.
The polymers or co-polymers of the present invention can comprise mixtures of linearly and cyclically polymerizing monomers, for example the poly(dimethyldiallyl-ammonium chloride/acrylamide) co-polymer having the formula:
wherein Z1, Z2, x, y, and z are the same as defined herein above and X is chloride ion.
A particularly preferred embodiment of this invention is the composition comprising a polymer based on dimethyldiallylammonium chloride and a copolymer which is based upon acrylamide with a co-monomer selected from the group consisting of N,N dialkylaminoalkyl(meth)acrylate, N,N dialkylaminoalkylacrylate, N,N dialkylaminoalkylacrylamide, N,N dialkylaminoalkyl(meth)acrylamide, their quaternized derivatives and mixtures thereof.
Non-limiting examples of preferred polymers according to the present invention include dye maintenance copolymers comprising:
i) a first monomer selected from the group consisting of N,N dialkylaminoalkyl(meth)acrylate, N,N dialkylaminoalkylacrylate, N,N dialkylaminoalkylacrylamide, N,N dialkylaminoalkyl(meth)acrylamide, their quaternized derivatives and mixtures thereof; and
ii) a second monomer selected from the group consisting of acrylic acid, methacrylic acid, C1-C6 alkylmethacrylate, C1-C6 alkyl acrylate, C1-C8 hydroxyalkylacrylate, C1-C8 hydroxyalkylmethacrylate, acrylamide, C1-C16 alkyl acrylamide, C1-C16 dialkylacrylamide, 2-acrylamido-2-methylpropane sulfonic acid or its alkali salt, methacrylamide, C1-C16 alkylmethacrylamide, C1-C16 dialkylmethacrylamide, vinyl formamide, vinylacetamide, vinyl alcohol, C1-C8 vinylalkylether, vinyl pyridine, itaconic acid, vinyl acetate, vinyl propionate, vinyl butyrate and mixtures thereof;
wherein the copolymer comprises at least 25 mole % of the first monomer.
Adjunct Ingredients
The compositions of the present invention may also optionally comprise one or more adjunct ingredients. Non-limiting examples of adjunct ingredients are selected from the group consisting of detersive surfactants, electrolytes, stabilizers, low molecular weight water soluble solvents, chelating agents, dispersibility aids, soil release agents, nonionic fabric softening agents, concentration aid, perfume, preservatives, colorants, optical brighteners, opacifiers, germicides, fungicides, anti-corrosion agents, antifoam agents, and mixtures thereof.
The following are applications which describe various detergent additive, methods of making these additives and methods of using them are all included herein by reference. WO 99/07813 A1 Randall et al., xe2x80x9cLaundry Detergent Compositions with Amino Acid Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewithxe2x80x9d; WO 99/07814 A1 Randall et al., xe2x80x9cLaundry Detergent Compositions with Amino Acid Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laudered Therewithxe2x80x9d; WO 99/14299 A1 Panandiker et al., xe2x80x9cLaundry Detergent Compositions with Anionically Modified, Cyclic Amine Based Polymers; WO 99/14300 A1 Panandiker et al., xe2x80x9cLaundry Detergent Compositions with Cyclic Amine-Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewithxe2x80x9d; WO 99/14301 A1 Panandiker et al., xe2x80x9cLaundry Detergent Compositions and Fabric Conditioning Compositions with Oxidized Cyclic Amine-Based Polymersxe2x80x9d; and U.S. 99/23146 Panandiker et al., xe2x80x9cLaundry Detergent Compositions with A Combination of Cyclic Amine Based Polymers and Hydrophobically Modified Carboxy Methyl Cellulosexe2x80x9d.
Surfactant System
The laundry detergent compositions of the present invention comprise a surfactant system. The surfactant systems of the present invention may comprise any type of detersive surfactant, non-limiting examples of which include one or more mid-chain branched alkyl sulfate surfactants, one or more mid-chain branched alkyl alkoxy sulfate surfactants, one or more mid-chain branched aryl sulfonate surfactants, one or more non mid-chain branched sulphonates, sulphates, cationic surfactants, zwitterionic surfactants, ampholytic surfactants, and mixtures thereof.
The total amount of surfactant present in the compositions of the present invention is from about 4% by weight, preferably from about 10% more preferably from about 15% to about 60%, preferably to about 30% by weight, of said composition.
Nonlimiting examples of surfactants useful herein include:
a) C11-C18 alkyl benzene sulfonates (LAS);
b) C6-C18 mid-chain branched aryl sulfonates (BLAS);
c) C10-C20 primary, xcex1 or xcfx89-branched, and random alkyl sulfates (AS);
d) C14-C20 mid-chain branched alkyl sulfates (BAS);
e) C10-C18 secondary (2,3) alkyl sulfates as described in U.S. Pat. No. 3,234,258 Morris, issued Feb. 8, 1966; U.S. Pat. No. 5,075,041 Lutz, issued Dec. 24, 1991; U.S. Pat. No. 5,349,101 Lutz et al., issued Sep. 20, 1994; and U.S. Pat. No. 5,389,277 Prieto, issued Feb. 14, 1995 each incorporated herein by reference;
f) C10-C18 alkyl alkoxy sulfates (AExS) wherein preferably x is from 1-7;
g) C14-C20 mid-chain branched alkyl alkoxy sulfates (BAExS);
h) C10-C18 alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units;
i) C12-C18 alkyl ethoxylates, C6-C12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units, C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers inter alia Pluronic(copyright) ex BASF which are disclosed in U.S. Pat. No. 3,929,678 Laughlin et al., issued Dec. 30, 1975, incorporated herein by reference;
j) C14-C22 mid-chain branched alkyl alkoxylates, BAEx;
k) Alkylpolysaccharides as disclosed in U.S. Pat. No. 4,565,647 Llenado, issued Jan. 26, 1986, incorporated herein by reference;
l) Polyhydroxy fatty acid amides having the formula:
wherein R7 is C5-C31 alkyl; R8 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, Q is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof; preferred alkoxy is ethoxy or propoxy, and mixtures thereof; preferred Q is derived from a reducing sugar in a reductive amination reaction, more preferably Q is a glycityl moiety; Q is more preferably selected from the group consisting of xe2x80x94CH2(CHOH)nCH2OH, xe2x80x94CH(CH2OH)(CHOH)n-1CH2OH, xe2x80x94CH2(CHOH)2(CHORxe2x80x2)(CHOH)CH2OH, and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5, inclusive, and Rxe2x80x2 is hydrogen or a cyclic or aliphatic monosaccharide, which are described in U.S. Pat. No. 5,489,393 Connor et al., issued Feb. 6, 1996; and U.S. Pat. No. 5,45,982 Murch et al., issued Oct. 3, 1995, both incorporated herein by reference.
A non-limiting example of a nonionic surfactant suitable for use in the present invention has the formula:
wherein R is C7-C21 linear alkyl, C7-C21 branched alkyl, C7-C21 linear alkenyl, C7-C21 branched alkenyl, and mixtures thereof.
R1 is ethylene; R2 is C3-C4 linear alkyl, C3-C4 branched alkyl, and mixtures thereof; preferably R2 is 1,2-propylene. Nonionic surfactants which comprise a mixture of R1 and R2 units preferably comprise from about 4 to about 12 ethylene units in combination with from about 1 to about 4 1,2-propylene units. The units may be alternating, or grouped together in any combination suitable to the formulator. Preferably the ratio of R1 units to R2 units is from about 4:1 to about 8:1. Preferably an R2 units (i.e. 1,2-propylene) is attached to the nitrogen atom followed by the balance of the chain comprising from 4 to 8 ethylene units.
R2 is hydrogen, C1-C4 linear alkyl, C3-C4 branched alkyl, and mixtures thereof; preferably hydrogen or methyl, more preferably hydrogen.
R4 is hydrogen, C1-C4 linear alkyl, C3-C4 branched alkyl, and mixtures thereof; preferably hydrogen. When the index m is equal to 2 the index n must be equal to 0 and the R4 unit is absent and is instead replaced by a xe2x80x94[(R1O)x(R2O)yR3] unit.
The index m is 1 or 2, the index n is 0 or 1, provided that when m is equal to 1, n is equal to 1; and when m is 2 n is 0; preferably m is equal to 1 and n is equal to one, resulting in one xe2x80x94[(R1O)x(R2O)yR3] unit and R4 being present on the nitrogen. The index x is from 0 to about 50, preferably from about 3 to about 25, more preferably from about 3 to about 10. The index y is from 0 to about 10, preferably 0, however when the index y is not equal to 0, y is from 1 to about 4. Preferably all of the alkyleneoxy units are ethyleneoxy units. Those skilled in the art of ethoxylated polyoxyalkylene alkyl amide surface active agents will recognized that the values for the indices x and y are average values and the true values may range over several values depending upon the process used to alkoxylate the amides.
The mid-chain branched alkyl sulfate surfactants of the present invention have the formula:
the alkyl alkoxy sulfates have the formula:
the alkyl alkoxylates have the formula:
wherein R, R1, and R2 are each independently hydrogen, C1-C3 alkyl, and mixtures thereof; provided at least one of R, R1, and R2 is not hydrogen; preferably R, R1, and R2 are methyl; preferably one of R, R1, and R2 is methyl and the other units are hydrogen. The total number of carbon atoms in the mid-chain branched alkyl sulfate and alkyl alkoxy sulfate surfactants is from 14 to 20; the index w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1; provided w+x+y+z is from 8 to 14 and the total number of carbon atoms in a surfactant is from 14 to 20; R3 is C1-C4 linear or branched alkylene, preferably ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof. However, a preferred embodiment of the present invention comprises from 1 to 3 units wherein R3 is 1,2-propylene, 1,3-propylene, or mixtures thereof followed by the balance of the R3 units comprising ethylene units. Another preferred embodiment comprises R3 units which are randomly ethylene and 1,2-propylene units. The average value of the index m is at least about 0.01. When the index m has low values, the surfactant system comprises mostly alkyl sulfates with a small amount of alkyl alkoxy sulfate surfactant. Some tertiary carbon atoms may be present in the alkyl chain, however, this embodiment is not desired.
M denotes a cation, preferably hydrogen, a water soluble cation, and mixtures thereof. Non-limiting examples of water soluble cations include sodium, potassium, lithium, ammonium, alkyl ammonium, and mixtures thereof.
Detergent Builder
The detergent compositions herein may also comprise from about 0.1% to 80% by weight of a detergent builder. Preferably such compositions in liquid form will comprise from about 1% to 10% by weight of the builder component. Preferably such compositions in granular form will comprise from about 1% to 50% by weight of the builder component. Detergent builders are well known in the art and can comprise, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders.
Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates. Suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979 to Crutchfield et al., and U.S. Pat. No. 4,246,495, issued Mar. 27, 1979 to Crutchfield et al., both of which are incorporated herein by reference. Particularly preferred polycarboxylate builders are the oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Pat. No. 4,663,071, Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference.
Examples of suitable nonphosphorus, inorganic builders include the silicates, aluminosilicates, borates and carbonates. Particularly preferred are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of SiO2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Also preferred are aluminosilicates including zeolites. Such materials and their use as detergent builders are more fully discussed in Corkill et al., U.S. Pat. No. 4,605,509, the disclosure of which is incorporated herein by reference. Also discussed in U.S. Pat. No. 4,605,509 are crystalline layered silicates which are suitable for use in the detergent compositions of this invention.
Optional Detergent Ingredients
In addition to the surfactants, builders and dye maintenance polymers of the detergent compositions of the present invention can also include any number of additional optional ingredients. These include conventional detergent composition components such as enzymes and enzyme stabilizing agents, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, bleaching agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical brighteners, dyes and perfumes.
pH adjusting agents may be necessary in certain applications where the pH of the wash solution is greater than about 10.0 because the fabric integrity benefits of the defined compositions begin to diminish at a higher pH. Hence, if the wash solution is greater than about 10.0 after the addition of the dye maintenance polymers of the present invention a pH adjuster should be used to reduce the pH of the washing solution to below about 10.0, preferably to a pH of below about 9.5 and most preferably below about 7.5. Suitable pH adjusters will be known to those skilled in the art.
A preferred optional ingredients for incorporation into the detergent compositions herein comprises a bleaching agent, e.g., a peroxygen bleach. Such peroxygen bleaching agents may be organic or inorganic in nature. Inorganic peroxygen bleaching agents are frequently utilized in combination with a bleach activator.
Useful organic peroxygen bleaching agents include percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, Hartman, Issued Nov. 20, 1984; European Patent Application EP-A-133,354, Banks et al., Published Feb. 20, 1985; and U.S. Pat. No. 4,412,934, Chung et al., Issued Nov. 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in U.S. Pat. No. 4,634,551, Issued Jan. 6, 1987 to Burns et al.
Inorganic peroxygen bleaching agents may also be used, generally in particulate form, in the detergent compositions herein. Inorganic bleaching agents are in fact preferred. Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials. For example, sodium perborate (e.g. mono- or tetra-hydrate) can be used. Suitable inorganic bleaching agents can also include sodium or potassium carbonate peroxyhydrate and equivalent xe2x80x9cpercarbonatexe2x80x9d bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used. Frequently inorganic peroxygen bleaches will be coated with silicate, borate, sulfate or water-soluble surfactants. For example, coated percarbonate particles are available from various commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.
Inorganic peroxygen bleaching agents, e.g., the perborates, the percarbonate, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during use of the compositions herein for fabric laundering/bleaching) of the peroxy acid corresponding to the bleach activator. Various non-limiting examples of activators are disclosed in U.S. Pat. No. 4,915,854, Issued Apr. 10, 1990 to Mao et al.; and U.S. Pat. No. 4,412,934 Issued Nov. 1, 1983 to Chung et al. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical and preferred. Mixtures thereof can also be used. See also the hereinbefore referenced U.S. Pat. No. 4,634,551 for other typical bleaches and activators useful herein.
Other useful amido-derived bleach activators are those of the formulae:
R1N(R5)C(O)R2C(O)L
or
R1C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms. R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenol sulfonate.
Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzene-sul-fonate, (6-decanamido-caproyl)oxybenzenesulfonate and mixtures thereof as described in the hereinbefore referenced U.S. Pat. No. 4,634,551.
Another class of useful bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al. in U.S. Pat. No. 4,966,723, Issued Oct. 30, 1990, incorporated herein by reference. See also U.S. Pat. No. 4,545,784, Issued to Sanderson, Oct. 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
If utilized, peroxygen bleaching agent will generally comprise from about 2% to 30% by weight of the detergent compositions herein. More preferably, peroxygen bleaching agent will comprise from about 2% to 20% by weight of the compositions. Most preferably, peroxygen bleaching agent will be present to the extent of from about 3% to 15% by weight of the compositions herein. If utilized, bleach activators can comprise from about 2% to 10% by weight of the detergent compositions herein. Frequently, activators are employed such that the molar ratio of bleaching agent to activator ranges from about 1:1 to 10:1, more preferably from about 1.5:1 to 5:1.
Additional suitable bleaching agents and bleach activators are disclosed in one or more of the co-pending PCT Applications listed in Table A and incorporated herein by reference.
Another highly preferred optional ingredient in the detergent compositions herein is a detersive enzyme component. Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability, optimal thermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
xe2x80x9cDetersive enzymexe2x80x9d, as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry detergent composition. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases.
Enzymes are normally incorporated into detergent compositions at levels sufficient to provide a xe2x80x9ccleaning-effective amountxe2x80x9d. The term xe2x80x9ccleaning-effective amountxe2x80x9d refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher active levels may be desirable in highly concentrated detergent formulations.
Cellulases usable herein include those disclosed in U.S. Pat. No. 4,435,307, Barbesgoard et al., Mar. 6, 1984, and GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME(copyright) and CELLUZYME(copyright) (Novo) are especially useful. See also WO 9117243 to Novo.
The enzyme-containing compositions herein may optionally also comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes. Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
Detergent Composition Preparation
The detergent compositions according to the present invention can be in liquid, paste or granular form. Such compositions can be prepared by combining the essential and optional components in the requisite concentrations in any suitable order and by any conventional means. The forgoing description of uses for the dye maintenance polymers defined herein are intended to be exemplary and other uses will be apparent to those skilled in the art and are intended to be within the scope of the present invention.
Granular compositions, for example, are generally made by combining base granule ingredients, e.g., surfactants, builders, water, etc., as a slurry, and spray drying the resulting slurry to a low level of residual moisture (5-12%). The remaining dry ingredients, e.g., granules of the essential dye maintenance polymers, can be admixed in granular powder form with the spray dried granules in a rotary mixing drum. The liquid ingredients, e.g., solutions of the essential dye maintenance polymers, enzymes, binders and perfumes, can be sprayed onto the resulting granules to form the finished detergent composition. Granular compositions according to the present invention can also be in xe2x80x9ccompact formxe2x80x9d, i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/l. In such case, the granular detergent compositions according to the present invention will contain a lower amount of xe2x80x9cinorganic filler saltxe2x80x9d, compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; xe2x80x9ccompactxe2x80x9d detergents typically comprise not more than 10% filler salt.
Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations. Liquid compositions according to the present invention can also be in xe2x80x9ccompact formxe2x80x9d, in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. Addition of the dye maintenance polymers to liquid detergent or other aqueous compositions of this invention may be accomplished by simply mixing into the liquid solutions the desired dye maintenance polymers.
Fabric Laundering Method
The present invention also provides a method for laundering fabrics in a manner which imparts fabric appearance benefits provided by the dye maintenance polymers used herein. Such a method employs contacting these fabrics with an aqueous washing solution formed from an effective amount of the detergent compositions hereinbefore described or formed from the individual components of such compositions. Contacting of fabrics with washing solution will generally occur under conditions of agitation although the compositions of the present invention may also be used to form aqueous unagitated soaking solutions for fabric cleaning and treatment. As discussed above, it is preferred that the washing solution have a pH of less than about 10.0, preferably it has a pH of about 9.5 and most preferably it has a pH of about 7.5.
Agitation is preferably provided in a washing machine for good cleaning. Washing is preferably followed by drying the wet fabric in a conventional clothes dryer. An effective amount of a high density liquid or granular detergent composition in the aqueous wash solution in the washing machine is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm.

Laundry detergent compositions with certain cationically charged dye maintenance polymers


A data transmission system, in which a plurality of repeater nodes are interconnected by optical fiber or electrical transmission links, which has a predetermined bypass path split ratio and does not require an automatic gain control circuit. Each node includes an electrical splitter at its input, an active branch including a receiver and a transmitter, and a passive branch which bypasses the active path. The active and passive branches are joined at the output of the node by an electrical combiner. By choosing the splitting ratio of the electrical splitters to have approximately a 70/30 split, with 70% going to the active branch and 30% going to the passive branch, a 10.sup.-9 bit error rate is readily achievable.

1. Field of the Invention
This invention relates to a data transmission system in which a plurality of repeater nodes are interconnected by transmission links and, more particularly, to a system that has a predetermined bypass path split ratio and does not require an automatic gain control circuit.
2. Description of the Related Art
Fault tolerant systems for data transmission systems are known in the art. Conventional methods for providing fault tolerant systems include methods which bypass the main transmission path utilizing a bypass switch which, upon failure at a node, will allow a bypass around the failed node. Another method utilizes parallel redundant transmission equipment, thereby allowing use of a secondary system when a primary system fails. Chown et al., U.S. Pat. No. 4,166,946, teaches a data transmission system utilizing optical fibers in which an optical fiber bypass arrangement is provided in the event of a repeater node failure. In each of the above systems, the main signal input into the repeater is boosted and sent further down the line. This boosting is needed to cure the effect of signal degradation as the signal travels over the transmission line.
FIG. 1 is a graph conceptually showing how a repeater of the prior art affects a signal applied to its input. As shown in FIG. 1, a digital signal (line A), which has degraded due to propagation losses, is applied to the input. In the repeater, the signal is boosted by adding to the input signal (portion C in FIG. 1), thus raising the amplitude of the signal so that it is output as shown by dotted line B. A major problem in implementing such a boosting scheme is the accuracy by which the boosted signal is added to the original signal. Also, an optically incoherent boost scheme cannot improve the accumulation of pulse dispersion.

Fault tolerant data transmission network


A sample acquiring device for volumetric enumeration of white blood cells in a blood sample that includes a measurement cavity for receiving a blood sample. The measurement cavity has a predetermined fixed thickness. The sample acquiring device also has a reagent, which is arranged in a dried form on a surface defining the measurement cavity. The reagent has a hemolysing agent for lysing red blood cells in the sample and a staining agent for selectively staining white blood cells in the sample. Also, a system with the sample acquiring device and a measurement apparatus. The measurement apparatus has a sample acquiring device holder, a light source, and an imaging system for acquiring a digital image of a magnification of the sample The measurement apparatus also has an image analyzer arranged to analyze the acquired digital image for determining the number of white blood cells in the blood sample.

Determining a white blood cell count is often important in connection to treating a patient. This analysis may be needed for diagnosing e.g. leukemia, or infectious or inflammatory diseases or for monitoring treatments. It is desirable to enable analysis results to be obtained as quickly as possible in order to minimize waiting times for patients and enabling a physician to make a decision of treatment and diagnosis directly when making a first examination of the patient. It would therefore be preferable to provide an analysis method which may be quickly performed by the physician or a nurse without the need of sending a test away to a laboratory.
Today, a white blood cell count is normally obtained by staining a blood sample and microscopically viewing the sample in a special counting chamber, e.g. a Bürker chamber. The counting chamber is provided with a grid dividing the chamber in well-defined small volumes. The white blood cell count can then be determined by counting the number of blood cells per box in the grid. The white blood cell count is obtained manually by an analyst, who needs to be experienced in performing the analysis in order to be able to perform a reliable analysis.
This analysis is time-consuming. Further, since it is performed manually, the results of the analysis may vary depending on the person performing the analysis.
There are a few number of existing automated analysis methods for determining a white blood cell count. The white blood cell count may be determined by means of the Coulter principle, which is based on determining cell size and thereby the cell type by sensing an impedance. A method for counting white blood cells by the Coulter principle is described in U.S. Pat. No. 5,262,302.
Another method for determining a white blood cell count is disclosed in U.S. Pat. No. 5,585,246. Here, a blood sample has to be prepared by being mixed with a fluorescent dye and ligand complex which tags the white blood cells. The sample is introduced into a capillary and is irradiated by a laser source which scans over the sample in the capillary. The fluorescence is measured in order to determine the number of white blood cells.
In WO 99/45384, a sample containing chamber having varying thickness is shown. The varying thickness separates different compounds of blood. The blood sample is stained with a colorant to differentially highlight at least three different white blood cell types in the blood sample. The white blood cells may be enumerated by using an optical scanning instrument to view a portion of the chamber.
There is still a need to speed up and simplify existing automated methods for determining a white blood cell count such that analysis may be provided at point of care.


A ratchet socket may include a main body, and an outer periphery of the main body has ratchet teeth formed in an endless circular pattern to form the main body with a polygonal cross section. The main body comprises a hexagonal inner periphery to form six internal angles and six inner edges. Each of the inner edges has an engaging portion at a middle portion thereof, and each of the inner edges comprises two abutting portions at two sides of the engaging portion between the engaging portion and each of two adjacent internal angles. Each of two recess portions is formed between the engaging portion and the abutting portion to form two engaging teeth on two lateral edges of the engaging portion. Each of the internal angles is curved to form an inclined surface between the abutting portion and the adjacent internal angle.

A conventional tool such as ratchet wrench comprises a driving head (40) that has a hexagonal tool slot (41) (or clamp hole), and a user is adapted to engage the clamp slot with a lock unit (50) having a hexagonal head portion (51) and apply force to loosen or tighten the lock unit.
In order to engage easily with the head portion (51) of the lock unit (50), the inner diameter of the tool slot (41) of the driving head (40) is manufactured slightly larger than the indicated size, and the head portion (51) of the lock unit (50) is configured to have the outer diameter thereof slightly smaller than the indicated size, thereby engaging the driving head (40) with the lock unit (50) easily (as shown in FIGS. 14 to 16). However, although the larger inner diameter of the tool slot (41) and the smaller outer diameter of the head portion (51) can easily engage the driving head (40) and the lock unit (50) together, it also forms the larger gap between the tool slot (41) and the head portion (51) after coupled together. As a result, the slipping out may happen when the force applies on the driving head (40) to turn the head portion (51) of the lock unit (50) so as to damage the inner wall of the tool slot (41) and the head portion (51), leading to reducing the lifetimes of the lock unit (50) and the driving head (40).
Referring to FIGS. 17 to 19, in order to solve the problem mentioned above, there is a ratchet socket in the market comprising a socket (60), and an inner periphery of the socket (60) is formed into a hexagonal shape connecting hole (61) to engage with a screw unit. Each of six edges of the connecting hole (61) is formed into a connecting portion (62), and a middle portion of the connecting portion (62) has a stepped-shaped driving portion (621). When the socket (60) is used, the driving portion (621) forms an acute angle toward the counterclockwise direction, and the wall thickness of the connecting portion in the counterclockwise direction is thinner than that in the clockwise direction. Moreover, a plurality of connecting edges (63) are formed on an outer periphery of the socket (60), the length and the angle of each connecting edge (63) are the same. An opening of a tool is adapted to engage with the connecting edges (63) to enable the tool to provide torque, and the socket (60) is adapted to dispose on the screw unit, and the driving portion (621) of the connecting portion (62) is adapted to engage and rotate the screw unit, so as to loosen or tighten the screw unit.
However, the conventional ratchet socket has following disadvantages: (i) with the stepped-shaped driving portions (621), the normal and corresponding screw unit cannot be fitted, and the driving portions (621) can only be rotated in the counterclockwise direction, which greatly reduces consumer purchase intention; and (ii) the length and the angle of each connecting edge (63) of the socket (63) are the same, and when the opening of the tool is connected to the socket (60) to provide torque, the force is configured to apply on each corner of the connecting edge (63), and the wall thickness of the counterclockwise corners of the connecting portions (62) is relative thin due to the driving portions (621), so that it is easy to cause wear and fracture in the counterclockwise corner under the situation of torsion loosening, which results in poor durability and lack of practicality. Therefore, there remains a need for a new and improved design for a ratchet socket to overcome the problems presented above.


A device includes a ring having a tubular interior surface centred about an axis. The surface includes a plurality of axially extending, inwardly-projecting ridges. On opposite sides of each ridge is a first port and a second port. A rotor rotates in the ring about the axis. A plurality of vanes is mounted to the rotor body for rotation therewith and for radial extension and retraction relative thereto such that the surface can be swept by the vanes. The rotor and the ring are sealed to permit fluid communication into and out of the device only via the ports. The vanes retract and extend as the body rotates such that chambers are created which decrease in volume when in communication with the first ports and chambers are created which increase in volume when in communication with the second ports. A fluid pressure mechanism can cause vane retraction.

Vane pumps are well-known positive-displacement pumps. A simple vane pump consists of a rotor positioned inside a larger circular cavity. The rotation axis is offset from the axis of the cavity and vanes are allowed to slide into and out of the rotor and seal on all edges. This creates, on one side of the pump, vane chambers that increase in volume. These increasing volume vane chambers are filled with fluid forced in by the inlet pressure. Often this inlet pressure is nothing more than pressure from the atmosphere. On the discharge side of the pump, there are created vane chambers which decrease in volume. This forces fluid out of the pump. Typically, these pumps run at relatively high speeds, and the centrifugal force associated with the rotation is used to hold the vanes against the surface of the interior cavity for sealing. While vane pumps are known to have utility, many suffer from a disadvantageous combination of relatively high cost and relatively low longevity.


A method (10) and system (50) for using a biometrically enabled password can include an input device (58) capable of entering a password entry and a processor (56) coupled to the input device. The processor can monitor (16 or 26) a cadence such as monitoring a keystroke signature, store the cadence of the password entry, compare (28) the cadence of a subsequent password entry with the cadence of at least one previous password entry, establish (30) a stability metric with respect to the cadences compared, and require (32) both the password entry and the cadence once the cadence meets the stability metric. The processor can require only the password entry until the stability metric for the cadence is achieved. The processor can also determine (14) if the password entry is new and optionally require (18) only the password entry to enter the system if determined as new.

1. Technical Field
This invention relates to the field of password entry systems, and more particularly to a method and system for establishing a biometrically enabled password.
2. Description of the Related Art
Numerous conventional password entry systems exist that monitor keystroke dynamics as a biometric input, where keystroke dynamics can refer to pauses between key presses and key press combinations, duration of key presses, etc. that together form a typing signature that can be used to identify a user. Conventional password entry systems can require a constant monitoring of keystroke dynamics and can require that password entry occur in a fashion consistent with a characteristic keystroke dynamic recorded for an associated user. One drawback of such as system is that it can require users to complete an enrollment process before the users are granted access to the secured system, assuming that the enrollment processes establish a keystroke dynamic for the user.
Further, existing or known systems ignore the fact that for some period of time after creating a new password, a user's keystroke dynamics are not likely to be stable. A user entering a password with multiple characters will typically fail to consistently use the same cadence or pattern of keystrokes, particularly for a newly or recently created password. That is, until a password is "well known" a user can often pause (even slightly) in the entry of the password, which can cause the keystroke dynamics for the password to be different than that user's typical keystroke dynamics.
This difference can be especially pronounced when a strong password is used. A strong password in this context can be a long string of characters, but can also be a short but unusual combination of letters and/or numbers or other characters, the entry of which can cause the user's keystroke dynamics to be abnormal. The stronger the password, the longer the expected time to reach password production stability because strong passwords deliberately avoid stereotypical patterns of characters, which inhibits normal typing patterns. The problem with keystroke dynamics being initially unstable for a password has either not been identified within the field or not addressed as no existing password entry system (as currently known to the inventors herein) holds back on applying a keyboard biometric to a password until biometric characteristics have stabilized or become more consistent.

Method and system for establishing a biometrically enabled password


According to the method of the invention, the movement of movable screen ends for a group of motor-driven screens to a common position is controlled in a grouped manner. The method includes a step (E150) consisting of moving the end of a screen when said end becomes the farthest from the common position after moving the end of at least one other screen to said common position.

1. Field Of The Invention
The present invention relates to a group control method for controlling as a group a plurality of motor-driven screens equipped with respective bottom weighting bars or "load bars". Such screens may be venetian blinds or shades or other analogous blinds or shades. This type of screen is provided with a least one raising cord, connected to the load bar, and winding around a shaft driven in rotation by an actuator. The screens may also be roll-up fabric blinds or shades, or indeed roller blinds or roller shutters. In any event it is necessary for the position of the load bar of a screen to be measured as independently as possible from the position of the screen.
2. Brief Description Of The Related Art
In order to drive a plurality of motor-driven screens, it is known that automatic motor control can be used that makes it possible to manage the screen positions and/or the slat angular positions of the screens of the group in such a manner that each screen has the same screen position and/or the same slat angular position after a group command. The driving is generally achieved by operation of the "master-and-slave" type in which a "master" screen drives the "slaves", i.e. the other screens of the group. The slave screens reproduce the configuration, i.e. the screen position and/or the slat angular position of the master screen, as described in Application JP-A-08210054. As specified in EP-A-0 913 748, the screen position and/or the slat angular position of a screen can be adjusted by calculating motor or time pulses by means of a microprocessor. Correspondence between those pulses and screen position or slat angular position may be defined directly.
The stroke of a screen is determined by the distance travelled by the load bar between first and second predetermined positions. The first position or "upper limit" generally corresponds to a load bar position in which the screen is fully open. The load bar then reaches a top abutment. The top abutment is a stop position desired by the user. The second position or "down limit" corresponds to a load bar position such that the screen is fully closed. The load bar then reaches a bottom abutment. In the preceding patent applications, all of the screens have substantially the same stroke and the same upper limit positions.
The position of the load bar of a screen is measured relative to a predetermined reference position. In addition, a calibration operation may be provided that makes it possible to define the same reference position for all of the screens of the group after installation. Such a reference position is described as a common specific position corresponding to all of the tops-of-stroke of the screens in the group.
Thus, when a load bar movement instruction is executed for moving the load bars to a precise desired position of the screen stroke, each load bar of the screens of the group moves towards that position defined relative to the common reference position. At the end of the operation, all of the load bars lie at the same position and are aligned. However, if the load bars of the screens of the group are not aligned at the time the instruction is issued, then each load bar moves independently from the other load bars. That results in the movements of the screens of the group not being harmonious due to the variations in amplitudes of movement of the load bars. In addition to the unpleasing appearance, such unevenness does not make it possible to have rapidly information about the synchronization of the screens, and in particular of their counter means, or about the screening states of the other screens in the group.
The same applies when a group command for opening or for closure is executed for a group of screens in which the load bars are not aligned. Alignment of the load bars can be obtained in the end limit position, after movements of various amplitudes.
Alignment of the load bars of roller blinds during an operation is known from US-A-2005/0173080 that describes speed compensator means for two screens of different configurations, which means act so that the load bars of both screens move level with each other when they are caused to move simultaneously. However, when those load bars are not initially level with each other, that system does not make it possible to align the load bars while they are moving.

Group control method for controlling motor-driven screens as a group, automatic motor control for implementing the method, and home automation installations including such automatic motor control


A food composition for consumption by mammals is designed to increase the production of glutathione peroxidase and superoxide dismutase. A serving of the food composition has a total weight and includes, in order of decreasing weight, a meat, a brassica vegetable, and brown rice.

1. Technical Field
This disclosure relates generally to a feed composition, and more specifically to an animal feed composition formulated to provide increased production of glutathione peroxidase and superoxide dismutase.
2. Description of the Related Art
The Merriam-Webster Medical Dictionary (2002) defines a carotenoid as any of various usually yellow to red pigments (as carotenes) found widely in plants and animals and characterized chemically by a long aliphatic polyene chain composed of eight isoprene units.
The Merriam-Webster® Medical Dictionary (2002) defines a methionine as a crystalline sulfur-containing essential amino acid C5H11NO2S that occurs in the L-form as a constituent of many proteins (as casein and egg albumin), that is important especially as a source of sulfur for the biosynthesis of cysteine and as a source of methyl groups for transmethylation reactions (as in the biosynthesis of choline, creatine, and adrenaline), and that is used as a dietary supplement for human beings and their domestic mammals and poultry and in the treatment of fatty infiltration of the liver.
The Merriam-Webster® Medical Dictionary (2002) defines a cysteine as a sulfur-containing amino acid C3H7NO2S that occurs in many proteins and glutathione and that is readily oxidizable to cystine.
The Merriam-Webster® Medical Dictionary (2002) defines an antioxidant as any of various substances (as beta-carotene, vitamin C, and alpha-tocopherol) that inhibit oxidation or reactions promoted by oxygen and peroxides and that include many held to protect the living body from the deleterious effects of free radicals.
The Merriam-Webster® Medical Dictionary (2002) defines glutathione as a peptide C10H17N3O6S that contains one amino acid residue each of glutamic acid, cysteine, and glycine, that occurs widely in plant and animal tissues, and that plays an important role in biological oxidation-reduction processes and as a coenzyme.
The Merriam-Webster® Medical Dictionary (2002) defines peroxidase as an enzyme occurring especially in plants, milk, and white blood cells and consisting of a protein complex with hematin groups that catalyzes the oxidation of various substances by peroxides.
The Merriam-Webster® Medical Dictionary (2002) defines superoxide dismutase as a metal-containing antioxidant enzyme that reduces potentially harmful free radicals of oxygen formed during normal metabolic cell processes to oxygen and hydrogen peroxide—abbreviation SOD.
The Merriam-Webster® Medical Dictionary (2002) defines an international unit as the amount of specific physiological activity of a standardized preparation (as of a vitamin) that is agreed upon as an international standard especially for comparison with other biologicals containing the substance in impure form or with a related biologically active substance; also: the amount of the biologically active substance in the standard amount of the preparation producing this activity.

Animal feed composition for increased production of glutathione peroxidase and superoxide dismutase


The present disclosure discloses a control method for an air conditioning system. The air conditioning system at least includes a compressor, a heat exchanger and a throttle device. The operation phase of the air conditioning system at least includes a start-up phase and a stable phase. The control method includes an action that in the start-up phase, the operating time of the compressor is set as t, when t is greater than 0 and less than 60s, an operating frequency F of the compressor is controlled to be less than 75 Hz, and a frequency rise speed per second Vf of the compressor is controlled to be less than 1.25 Hz/s.

In the currently used air conditioning system, when a heat exchanger in the system includes a multi-channel heat exchanger, the heat exchange performance of the multi-channel heat exchanger is poor at the start-up phase of the compressor, the heat exchanger is easily frosted during heating operation, which accelerates attenuation of the system capability during the heating operation.

Control method for air conditioning system, and air conditioning system

SANHUA (HANGZHOU) MICRO CHANNEL HEAT EXCHANGER CO., LTD.


A computing device includes a control system that communicates with multiple sensors that capture data regarding a user. The control system communicates with each of the sensors to obtain information regarding the capabilities of each sensor, and uses this capability information to determine how to configure each of the sensors. The control system also selects one of the multiple sensors to be the master sensor, and the rest of the multiple sensors are slave sensors, and notifies the multiple sensors of whether they are a slave sensor or a master sensor. The master sensor collects sensor data for the multiple sensors, capturing data itself as well as receiving data captured by the slave sensors from the slave sensors. The master sensor sends an indication of the collected data (e.g., the collected data itself or data resulting from processing the collected data) to the control system for analysis and/or processing.

As technology has advanced, computing devices have become increasingly mobile. For example, wireless phones, tablets, and headsets (e.g., virtual reality or augmented reality glasses) have become increasingly commonplace. These mobile computing devices can also oftentimes communicate with other devices (e.g., sensors) that the user is wearing. For example, a wristband may provide the number of steps a user has taken to a mobile computing device. All of these devices are powered by batteries, which eventually need recharging or replacing. However, having devices need their batteries recharged or replaced too frequently can lead to user frustration and dissatisfaction with their devices.

This patent is subject to a terminal disclaimer.

Multipoint sensor system for efficient power consumption


A light isolator member of an embodiment of the present invention is configured to be joined to another light isolator member to serve as a part of a light isolator, the light isolator member including: a lens surface disposed in a first surface; a transmission surface disposed at a position corresponding to the lens surface in a second surface on a side opposite to the first surface; and a fitting part disposed in the second surface, the fitting part being configured for fitting to the other light isolator member.

A laser device such as a semiconductor laser is used for optical communications using an optical transmission member such as an optical fiber and a light waveguide. In such a laser device, when light reflected by an optical surface or a processed surface disposed outside a laser resonator is returned, laser oscillation tends to become unstable, and may be resulted in signal noise in optical communications. Therefore, to prevent returning of reflected return light to the laser device, a light isolator including a Faraday rotator and a polarization light separating element is used, for example.
FIG. 1 is a schematic view illustrating light isolator 20 disclosed in PTL 1. As illustrated in FIG. 1, light isolator 20 includes a first optical fiber collimator including polarization maintenance optical fiber 1, collimator lens 3, and collimator lens holder 5, a second optical fiber collimator including polarization maintenance optical fiber 2, collimator lens 4 and collimator lens holder 6, and diffraction grating type polarizer 8, Faraday rotator 11 (sapphire substrate 14/garnet film 13/sapphire substrate 14) and light detector 10 disposed therebetween. In addition, light isolator 20 further includes shield plate 7 disposed between collimator lens 1 and diffraction grating type polarizer 8 of the first optical fiber collimator.
To assemble such a light isolator 20, it is necessary to accurately align the optical axis between polarization maintenance optical fiber 1 (or 2) and collimator lens 3 (or 4), for example.

Light isolator member and light isolator


A fuel evaporation quantity is estimated based on engine speed and opening degree of a throttle valve. The quantity of fuel to be injected is provided based on the estimated fuel evaporation quantity. A weight for a weighted mean is changed in accordance with the engine operating condition. A smoothed fuel injection quantity is provided by the weighted mean with the weight.

The present invention relates to a system and method for controlling fuel injection in an automotive engine having a single point injector, and more particularly to the system and method for controlling the quantity of fuel to be injected in accordance with a transport model of the fuel.
In a fuel injection system provided with a single fuel injector in a throttle body provided in an intake passage, injected fuel is induced in cylinders of the engine through the intake passage. A part of the fuel passing through the intake passage adheres to the wall of the passage to form a fuel film thereon. The fuel adhered to the wall eventually evaporates and is induced in the cylinders together with the injected fuel, which causes a difference between the quantity of the injected fuel calculated in dependency on engine operating conditions and the quantity actually induced in the cylinders of the engine. In order to control the actual quantity induced in the cylinders to a desired quantity, a fuel injection system has been proposed where the amount of fuel adhered to the wall of the intake passage and the rate of evaporating fuel thereof are estimated based on the fuel transport model to correct the quantity of fuel to be injected. Japanese Patent Laid-Open No. 61-126337 discloses a fuel injection system where a fuel injection quantity Gf is calculated based on a desired fuel quantity Qa/(A/F), a quantity of evaporated fuel Mf/.tau., a rate (1-x) of the quantity of fuel induced into the cylinders of the engine without adhering to the wall of the intake passage.
The prior art discloses a system for providing only a basic fuel injection quantity. Since there are various noise sources such as a spark plug in an engine compartment, the output signals of various sensors such as an engine speed sensor and a throttle position sensor can be affected by the noises. Consequently, the fuel injection quantity which is calculated based on engine speed and a throttle position is miscalculated, and hence, in particular in an engine with a single point injector, the fuel injection quantity oscillates, which causes deterioration of emission control and driveability.
To solve such a problem, the calculated fuel injection quantity should be filtered, for example by performing a weighted mean method. However, if a weight is constant regardless of the engine operating condition, the response of the engine speed in a transient state is delayed.

Fuel injection control system for an automotive engine


The invention provides a component feeding device where heat generation of a drive circuit is minimized and a printed board mounted with this drive circuit is miniaturized by forming an inexpensive structure using a single microcomputer and by energizing each of the servomotors only when necessary. In a component feeding unit of a dual lane type, a CPU in a microcomputer controls a start of driving of one of servomotors by energizing the servomotor through a drive circuit based on a component feeding signal for one lane outputted from a CPU of an electronic component mounting apparatus, and the CPU in the microcomputer controls one of the servomotors so that the servomotor is not energized when a component feeding signal for another lane is inputted before a predetermine time passes after a delay timer starts timekeeping when receiving a detection signal about rotation of the servomotor by a predetermined amount from an encoder detecting a rotation amount of the servomotor.

1. Field of the Invention
The invention relates to a component feeding device having a plurality of lanes each intermittently advancing a storage tape having electronic components stored in its storage portions to a component pickup position by each of servomotors.
2. Description of the Related Art
Generally, in a component feeding device intermittently advancing a storage tape having electronic components stored in its storage portions to a component pickup position, the storage tape can be advanced by any pitches by using a servomotor serving as a drive motor for advancing the storage tape. A printed board mounted with a drive circuit for driving the servomotor is built in the component feeding device. The relevant technology is described in the Japanese Patent Application Publication No. 2000-77892.
However, it costs much to form the component feeding device having a plurality of lanes each intermittently advancing the storage tape having the electronic components in its storage portions to the component pickup position by each of the servomotors, such as a component feeding device of a dual lane type. This is because the printed board built in such a component feeding device is mounted with microcomputers each provided for each of the servomotors.
Furthermore, in this case, the drive circuit generates high heat when a positioning loop is executed in each of the servomotors all the time to keep the servomotors ON (energized). This causes a dilemma between realizations of a compact feeding device and a design for heat radiation, thereby causing limitation in miniaturization of the printed board or the electronic component feeding device.


A method for detecting an electrically and/or magnetically conductive object in a vicinity of a sensor head of a device, having the following steps:                emitting a transmitting signal into the surroundings,        receiving a received signal as a function of the transmitting signal and the characteristics of the object and the surroundings,        analyzing a response signal formed from the received signal.

In the construction sector and auxiliary sectors, and also in the case of renovation measures, such a detection device, also referred to as a metal detector, is used, for example, to check whether or not a wall to be drilled through contains metallic objects. In general, a detection device may be used for locating electrically conductive objects, for example, also pipelines, in the floor or in a wall.
A device mentioned at the outset, which is also referred to hereafter as a detection device, may fundamentally be based on various measuring principles. One measuring principle is formed using a so-called continuous wave method, in which a continuous, typically low-frequency current is generated in a transmitting coil in the frequency range of several tens of kilohertz. With the aid of a receiving coil, a received signal, which arises due to an electromagnetic coupling between an electrically conductive object in the substrate and the emitted signal, is received and typically analyzed in the spectral range. In this measuring principle, either one measuring signal of a single frequency or a measuring signal which includes signal components in various frequency ranges is emitted. A detection device which is based on the above-described measuring principle is also referred to as a CW metal detector, CW standing for "continuous wave."
A detection device may also be based on a so-called pulse induction measuring principle. A pulse generator typically generates a pulse-like electrical current, which is applied to a coil of a transmitter, also referred to as a transmitting coil. A pulsed magnetic field is thus generated, which impinges on a conductive object located in the substrate. According to electromagnetic interactions, the pulsed magnetic field induces an eddy current in the electrically conductive object, which decays after a certain time as a function of the transmitter current pulse pattern. The induced eddy current in the electrically conductive object then generates a secondary magnetic field, which is received by a receiver, e.g., a coil, in the detection device. This secondary magnetic field is typically received with the aid of a coil of the receiver referred to as a receiving coil, in which the secondary magnetic field induces a receive current, which is then amplified by an amplifier connected downstream from the receiving coil. The amplified received signal is conducted to a so-called gate, which represents a barrier with respect to time. The gate is operated by a previously known detection device in such a way that it is only open for a very specific period of time after the application of a current pulse to the transmitting coil. For example, a delay unit is connected between the pulse generator and the gate, which prompts an opening of the gate after a fixed time after the triggering of the transmitter current pulse. The function of the gate is thus to eliminate an influence of the directly received transmitting pulse and it allows the receiving coil to nonetheless detect the secondary magnetic field. The output signal of the gate is typically integrated by an integrator, which sums the cumulative signal over multiple pulses and makes this signal available for a display device. A detection device which is based on this measuring principle is also referred to as a PI metal detector, PI standing for "pulse induction."
One or the other of the two above-described measuring principles is alternately implemented as a function of the field of use of the detection device and as a function of requirements which are placed on the detection device, for example, precision and/or power consumption. A metal detector, which may carry out both the CW and also the PI measuring principle, is known from the publication DE 699 17 030 T2. The metal detector described therein has a transmitter unit having a number of transmitting coils and a receiver unit having a number of receiving coils. In addition, the metal detector includes a so-called signal processing apparatus for correcting shifts in the case of measured components of received magnetic field gradients. For example, a received signal which has been distorted due to an incorrect orthogonal alignment of receiving coils in the receiver of the metal detector is thus post-corrected. However, this may be very time-consuming.

Method and device for detecting a conductive object

Abstract: According to the invention, the detection is controlled by                providing a class system having a number of classes, which differ from one another in at least one object and/or surroundings characteristic, and        classifying instantaneous object and/or surroundings characteristics as a function of the analyzed response signal in a class of the class system, and        predefining detection characteristics which are preset in the classified class, a further response signal being detected using the predefined detection characteristics.


This invention relates to a recombinant DNA molecule containing a gene or genes which encode a biocatalyst capable of desulfurizing a fossil fuel which contains organic sulfur molecules. For example, the present invention encompasses a recombinant DNA molecule containing a gene or genes of a strain of Rhodococcus rhodochrous.

Sulfur contaminants in fossil fuels can create problems in refinery processes which can be costly to rectify. The sulfur contaminants that occur in fossil fuels fall into either of the following general classes: mineralized (inorganic, e.g., pyritic) sulfur and organic sulfur (sulfur that is covalently bound to carbonaceous molecules, referred to as organosulfur compounds). The presence of sulfur has been correlated with corrosion of pipeline, pumping and refining equipment, and with premature breakdown of combustion engines. Sulfur also poisons many catalysts which are used in the refining of fossil fuels. Moreover, the atmospheric emission of sulfur combustion products, such as sulfur dioxide, leads to the form of acid deposition known as acid rain. Acid rain has lasting deleterious effects on aquatic and forest ecosystems, as well as on agricultural areas located downwind of combustion facilities. Monticello, D. J. and W. R. Finnerty, (1985) Ann. Rev. Microbiol, 39:371-389. Regulations such as the Clean Air Act of 1964 require the removal of sulfur, either pre- or post-combustion, from virtually all coal- and petroleum-based fuels. Conformity with such legislation has become increasingly problematic due to the rising need to utilize lower grade, higher-sulfur fossil fuels as clean-burning, low-sulfur petroleum reserves become depleted, as well as the progressive reductions in sulfur emissions required by regulatory authorities. Monticello, D. J. and J. J. Kilbane, "Practical Considerations in Biodesulfurization of Petroleum", IGT's 3d Intl. Symp. on Gas, Oil, Coal, and Env. Biotech., (Dec. 3-5, 1990) New Orleans, La.
One technique which is currently employed for the pre-combustion removal of organic sulfur from liquid fossil fuels, e.g., petroleum, is hydrodesulfurization (HDS). HDS is suitable for the desulfurization of fossil fuels wherein organosulfur compounds account for a significant, e.g., a major, proportion of all sulfur contaminants present. HDS is thus useful for treating crude oil or bitumen, petroleum distillate fractions or refining intermediates, liquid motor fuels, and the like. HDS is more particularly described in Shih, S.S. et al., "Deep Desulfurization of Distillate Components", Abstract No. 264B AIChE Chicago Annual Meeting, presented Nov. 12, 1990, (complete text available upon request from the American Institute of Chemical Engineers); Gary, J. H. and G. E. Handwerk, (1975) Petroleum Refining: Technology and Economics, Marcel Dekker, Inc., New York, pp. 114-120, and Speight, J. G., (1981) The Desulfurization of Heavy Oils and Residue, Marcel Dekker, Inc., New York, pp. 119-127. HDS is based on the reductive conversion of organic sulfur into hydrogen sulfide (H.sub.2 S) in the presence of a metal catalyst. HDS is carried out under conditions of elevated temperature and pressure. The hydrogen sulfide produced as a result of HDS is a corrosive gaseous substance, which is stripped from the fossil fuel by known techniques. Elevated or persistent levels of hydrogen sulfide are known to poison (inactivate) the HDS catalyst, complicating the desulfurization of liquid fossil fuels that are high in sulfur.
Organic sulfur in both coal and petroleum fossil fuels is present in a myriad of compounds, some of which are termed labile in that they can readily be desulfurized, others of which are termed refractory in that they do not easily yield to conventional desulfurization treatment, e.g., by HDS. Shih, S.S. et al. Frequently, then, even HDS-treated fossil fuels must be post-combustively desulfurized using an apparatus such as a flue scrubber. Flue scrubbers are expensive to install and difficult to maintain, especially for small combustion facilities. Moreover, of the sulfur-generated problems noted above, the use of flue scrubbers in conjunction with HDS is directed to addressing environmental acid deposition, rather than other sulfur-associated problems, such as corrosion of machinery and poisoning of catalysts.
Recognizing these and other shortcomings of HDS, many investigators have pursued the development of microbial desulfurization (MDS). MDS is generally described as the harnessing of metabolic processes of suitable bacteria to the desulfurization of fossil fuels. Thus, MDS typically involves mild (e.g., ambient or physiological) conditions, and does not involve the extremes of temperature and pressure required for HDS. It is also generally considered advantageous that biological desulfurizing agents can renew or replenish themselves under suitable conditions. Microbial desulfurization technology is reviewed in Monticello and Finnerty (1985), 39 ANN. REV. MICROBIOL. 371-389 and Bhadra et al. (1987), 5 BIOTECH. ADV. 1-27. Hartdegan et al. (1984), 5 CHEM. ENG. PROGRESS 63-67 and Kilbane (1989), 7 TRENDS BIOTECHNOL. (No. 4) 97-101 provide additional commentary on developments in the field.
Several investigators have reported mutagenizing naturally-occurring bacteria into mutant strains with the acquired capability of breaking down, i.e., catabolizing, dibenzothiophene (DBT). Hartdegan, F. J. et al., (May 1984) Chem. Eng. Progress 63-67. DBT is representative of the class of organic sulfur molecules found in fossil fuels from which it is most difficult to remove sulfur by HDS. Most of the reported mutant microorganisms act upon DBT nonspecifically, by cleaving carbon-carbon bonds, thereby releasing sulfur in the form of small organic breakdown products. One consequence of this microbial action is that the fuel value of a fossil fuel so treated is degraded. Isbister and Doyle, however, reported the derivation of a mutant strain of Pseudomonas which appeared to be capable of selectively liberating sulfur from DBT, thereby preserving the fuel value of treated fossil fuels. U.S. Pat. No. 4,562,156.
Kilbane recently reported the mutagenesis of a mixed bacterial culture, producing a bacterial consortium which appeared capable of selectively liberating sulfur from DBT by an oxidative pathway. Resour. Cons. Recycl. 3:69-79 (1990). A strain of Rhodococcus rhodocrous was subsequently isolated from the consortium. This strain, which has been deposited with the American Type Culture Collection under the terms of the Budapest Treaty as ATCC No. 53968 and also referred to as IGTS8, is a source of biocatalytic activity as described herein. Microorganisms of the ATCC No. 53968 strain liberate sulfur from forms of organic sulfur known to be present in fossil fuels, including DBT, by the selective, oxidative cleavage of carbon-sulfur bonds in organic sulfur molecules. Kilbane has described the isolation and characteristics of this strain in detail in U.S. Pat. No. 5,104,801.

Recombinant DNA encoding a desulfurization biocatalyst


Embodiments of the disclosure provide techniques for updating a distributed transaction log on a previously offline resource object component using distributed transaction logs from active host computer nodes from separate RAID mirror configurations. Each component object maintains a journal (log) where distributed transactions are recorded. If a component object goes offline and subsequently returns (e.g., if the node hosting the component object reboots), the component object is marked as stale. To return the component object to an active state, a distributed resources module retrieves the journals from other resource component objects from other RAID configurations where the data is mirrored. The module filters corresponding data that is missing in the journal of the previously offline corresponding object and merges the filtered data to the journal.

Distributed systems allow multiple clients in a network to access a pool of shared resources. For example, a distributed storage system allows a cluster of host computers to aggregate local disks (e.g., SSD, PCI-based flash storage, SATA, or SAS magnetic disks) located in or attached to each host computer to create a single and shared pool of storage. This pool of storage (sometimes referred to herein as a "datastore" or "store") is accessible by all host computers in the cluster and may be presented as a single namespace of storage entities (such as a hierarchical file system namespace in the case of files, a flat namespace of unique identifiers in the case of objects, etc.). Storage clients in turn, such as virtual machines spawned on the host computers may use the datastore, for example, to store virtual disks that are accessed by the virtual machines during their operation. Because the shared local disks that make up the datastore may have different performance characteristics (e.g., capacity, input/output operations per second or IOPS capabilities, etc.), usage of such shared local disks to store virtual disks or portions thereof may be distributed among the virtual machines based on the needs of each given virtual machine.
This approach provides enterprises with cost-effective performance. For instance, distributed storage using pooled local disks is inexpensive, highly scalable, and relatively simple to manage. Because such distributed storage can use commodity disks in the cluster, enterprises do not need to invest in additional storage infrastructure. However, one issue with such a distributed system is in failure recovery for nodes that return to the cluster after being offline for a period. For example, if a cluster node goes offline (e.g., due to a power outage), active and visible nodes in the cluster still perform regular transactions as designed, but one consequence of this is that if the offline node returns to the cluster, the node and corresponding resource component objects of the node are not up-to-date with the current state of the cluster and the operations previously performed on the component objects. In that state, the previously offline node is unusable in the cluster, which is ultimately inefficient because the distributed resources system is not using all of the resources available in the cluster.