text:
|Publication number
|Publication type
|Application number
|Publication date
|Sep 5, 2000
|Filing date
|Dec 23, 1997
|Priority date
|Dec 23, 1997
|Fee status
|Also published as
|Publication number
|Scott Hunter, Eugene R. Martin
|Original Assignee
|Wacker Silicones Corporation
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (15), Referenced by (17), Classifications (14), Legal Events (8)
|External Links: USPTO, USPTO Assignment, Espacenet
The present invention pertains to textile treating compositions and to a process for the treating of textile substrates with the composition, in particular to improve the softness thereof. More particularly, the present invention pertains to textile softening compositions comprising a nitrogen-functional organopolysiloxane and a polyisobutylene polymer.
Textile treating agents are utilized to treat fabrics to alter their properties, e.g. to provide a soft hand and feel. For example, emulsions of amino-functional organopolysiloxanes have been used as textile softening agents, as disclosed in U.S. Pat. No. 5,077,421. Such amino-functional silicone fluids may be prepared as described in U.S. Pat. Nos. 4,661,577 and 4,246,423. However, while the amino-functional organopolysiloxanes are efficient and commonly used textile treating agents, they are relatively expensive and, more importantly, are prone to discoloration, particularly yellowing.
The propensity of amino-functional organopolysiloxanes towards thermal yellowing has been recognized, and is discussed, for example, in U.S. Pat. No. 5,302,659, which discloses reacting an amino-functional organopolysiloxane with a carboxylic acid anhydride, in the presence of an emulsifier, in the aqueous phase. The products obtained through this reaction are stated to be acylated, amino-functional organopolysiloxane emulsions which have good storage stability and which are useful as textile finishing agents to provide treated textiles with good soft handle properties and a low tendency to thermal yellowing. However, the additional treatment required to prepare the acylated, amino-functional organopolysiloxanes renders these emulsions yet more expensive than the amino-functional polysiloxanes themselves.
Polybutene polymers are available as liquids and low melting solids which can be dispersed into water to form aqueous emulsions. Due to their low cost, polybutenes, and more specifically, polyisobutylenes, have been suggested for numerous uses as surface coatings, lubricants, etc. In U.S. Pat. No. 5,629,273, stable (non-phase separating) non-aqueous hydraulic fluids containing an organopolysiloxane fluid and a polybutene of identical viscosity were found to produce a hydraulic fluid with lower viscosity and good metal lubricity. In U.S. Pat. No. 5,507,960, emulsions of polyisobutylene and polydimethylsiloxanes are disclosed for treatment of leather, vinyl, and polymer surfaces to renew surface aesthetics, for example to renew automobile dashboards.
It would be desirable to provide compositions comprising emulsions of nitrogen-functional polysiloxanes suitable for use in fabric treating, particularly fabric softening, which exhibit a reduced tendency towards yellowing, which are cost effective as well, and which yet retain the beneficial characteristics of amino- and nitrogen-functional organopolysiloxanes.
The present invention pertains to fabric treating compositions comprising a nitrogen-functional organopolysiloxane and a polyisobutylene polymer. The inventive compositions can be emulsified just prior to application onto the substrate to be treated; may be prepared as a stable emulsion, particularly a micro-emulsion, which may be used as such or further diluted, as the case may be; or as a concentrate. Fabrics treated with the composition surprisingly exhibit less tendency towards yellowing, particularly after numerous wash cycles, while retaining soft hand.
The fabric treating compositions of the present invention comprise aqueous emulsions of a nitrogen-functional organopolysiloxane and a polyisobutylene polymer and concentrates suitable for the preparation thereof. More preferably, the emulsions of the subject invention are stable emulsions prepared by emulsifying one or more polyisobutylene polymers and at least one nitrogen-functional organopolysiloxane in the presence of suitable surfactants, cosolvents, and other adjuvants. When so prepared, the emulsions are stable and may be shipped and stored without separation. Preferred emulsions include those in which the polyisobutylene remains dispersed in the formulation, and those in which the nitrogen-functional organopolysiloxane contains pendant amino groups.
Suitable nitrogen-functional polyorganosiloxanes are well known to those skilled in the art and are available from numerous sources. One class of suitable nitrogen-functional organopolysiloxanes contain pendant aminoalkyl groups, and may contain at least one siloxane unit of the general formula: ##EQU1## and other siloxane units of the general formula: ##EQU2## in which each R1 may be the same or different, and represents a monovalent C1 to C18 hydrocarbon radical, a monovalent C1 to C18 hydrocarbon radical optionally substituted by one or more fluorine atoms; a hydrogen atom, a hydroxyl radical or alkyl glycol radical; or the group represented by R2 O wherein R2 may be the same as R1 above; and Q represents a group of the general formula:
--R3 --[NR3 (CH2)m ]d NHR4 (III)
hereinafter termed an "aminoalkyl group", in which R3 represents a divalent C1 to C18 hydrocarbon radical, R4 represents hydrogen, a C1 to C18 hydrocarbon radical, trialkylsilyl, particularly trimethylsilyl, or a fluorine-substituted C1 to C18 hydrocarbon radical, a has a value of 0, 1 or 2, b has a value of 1, 2 or 3, c has a value of 0, 1, 2, or 3, d has a value of 0, 1, 2, 3 or 4, m has a value of 2, 3, 4, 5 or 6 and the sum of a+b is no more than 4.
Non-limiting examples of C1 to C18 hydrocarbon radicals include radicals such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl or tert-pentyl radicals; hexyl radicals, such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical; and iso-octyl radicals such as the 2,2,4-trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; dodecyl radicals, such as the n-dodecyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl or cycloheptyl radicals and methylcyclohexyl radicals; aryl radicals, such as the phenyl radical and the naphthyl radical; alkaryl radicals, such as o-, m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical and the α- and β-phenylethyl radicals. The above hydrocarbon radicals optionally contain an aliphatic double bond. Examples are alkenyl radicals, such as the vinyl, allyl, 5-hexen-1-yl, E-4-hexen-1-yl, Z-4-hexen-1-yl, 2-(3-cyclohexenyl)-ethyl and cyclododeca-4,8-dienyl radical. Preferred radicals containing an aliphatic double bond are the vinyl, allyl and 5-hexen-1-yl radical. Preferably, however, not more than about 1% of the hydrocarbon radicals contain a double bond.
Non-limiting examples of C1 to C18 hydrocarbon radicals substituted by fluorine are the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2',2',2'-hexa-fluoroisopropyl radical, and the heptafluoroisopropyl radical.
Examples of divalent C1 to C18 hydrocarbon radicals represented by R3 are saturated straight-chain, branched, or cyclic alkylene radicals, such as the methylene, ethylene, propylene, butylene, pentylene, hexylene, 2-methylpropylene, cyclohexylene and octa-decylene radicals; or unsaturated alkylene or arylene radicals, such as the hexenylene radical and the phenylene radical, in which the n-propylene and the 2-methylpropylene radicals are particularly preferred.
The alkoxy radicals are alkyl radicals described above bonded via an oxygen atom. The examples for the alkyl radicals also apply to the alkoxy radicals. These examples of alkoxy radicals are illustrative and not limiting.
The alkyl glycol radicals represented by R1 preferably have the general formula:
--R3 --[O(CHR4)d ]n OR5 (IV)
in which R3, R4 and d are the same as above, n has a value of from 1 to 500 and R5 represents a hydrogen atom, a radical R4 or a group of the general formula ##STR1## where R6 represents the radical R4, or O--R4.
In the above general formulas (I) to (IV) R1 preferably represents a methyl, phenyl, C1 to C3 alkoxy or hydroxyl radical or a radical of the general formula (IV), R3 preferably represents a divalent C2 to C6 hydrocarbon radical. R4 preferably represents a hydrogen atom or a methyl radical, a preferably represents the value of 0 or 1, b preferably has a value of 1, c preferably has a value of 2 or 3 and d preferably has a value of 1.
Straight-chain nitrogen-functional polydimethylsiloxanes, which optionally have C1 to C3 alkoxy or hydroxyl end groups, or combinations thereof, are particularly preferred. In these polydimethylsiloxanes Q preferably represents a H2 N(CH2)2 NH(CH2)3 -- or H2 N(CH2)2 NHCH(CH3)CH2 -- group.
The ratio of the siloxane units of general formula (I) to the siloxane units of general formula (II) is preferably from 1:10 to 30000, and in particular from 1:20 to 300. The amine content is preferably from 0.001 to 2 meq/g, and in particular from 0.1 to 1.0 meq/g, measured as consumption of 1 N hydrochloric acid in ml/g organopolysiloxane (A) on titration to the neutral point.
It is possible to use only one type of organopolysiloxane (A). However, it is also possible to use a mixture of at least two different types of organopolysiloxane (A).
The organopolysiloxane (A) or a mixture of at least two different types of organopolysiloxane (A) preferably has an average viscosity of from 50 to 100,000 mPa�s, and more particularly from 100 to 10,000 mPa�s at 25� C.
Other nitrogen-functional organopolysiloxanes are suitable as well, as are also derivatives of such polysiloxanes, such as acylated amino-functional polysiloxanes as disclosed in U.S. Pat. No. 5,302,659, which is herein incorporated by reference. Also suitable are the amino-functional polysiloxanes disclosed in U.S. Pat. No. 5,077,421, which is also incorporated herein by reference. Due to the ability to include relatively inexpensive polyisobutylenes in the composition, these higher cost amino-functional organopolysiloxane derivatives may be used without excessive increase in cost.
Preferred amino-functional organopolysiloxanes correspond to the formula: ##STR2## where R7 is a trialkylsilyl group, preferably a trimethylsilyl group, hydrogen, or a monovalent hydrocarbon radical having 1-18 carbon atoms. Each R7 may be the same or different. In the dimethylsiloxy repeating units, k is from about 50 to 1000, preferably from about 500 to 800; and 1 is from about 1.0 to about 10, preferably 1 to about 3; and Q is as defined previously. Most preferably, k and 1 are about 211 and 2.1, respectively, or 275 and 1.5, respectively; and Q is
In the above formula, each R7 may also be an aminoalkyl group, in which case 1 may be from 0 to about 10. The above formulas represent the average molecule.
The nitrogen-functional organopolysiloxanes just described are eminently suitable for use in the subject invention. Amino-functional organopolysiloxanes having pendant aminoalkyl groups are preferred over organopolysiloxanes having only terminal amino functionality. However, other nitrogen-functional organopolysiloxanes may be used as well. By the term "nitrogen-functional" is meant organopolysiloxanes bearing functional groups containing nitrogen other than those having nitrogen directly bonded to silicon (silazanes). It has been found that in the absence of nitrogen-containing functional groups, organopolysiloxanes will not impart softness to textile fabrics treated there-with. Thus, for example, polydimethylsiloxanes having no nitrogen functionality, and bearing terminal trimethylsiloxy groups such as those taught by U.S. Pat. No. 5,507,960, or bearing alkoxydimethylsiloxy or dimethylsilanol groups are not suitable for use alone as fabric softeners.
The nitrogen-functional organopolysiloxanes may contain aminoalkyl groups, alkyl or aryl-substituted aminoalkyl groups, acylated aminoalkyl groups, amide groups, morpholino groups, pyrollidinyl groups, piperidinyl groups, imide groups, and the like. Further examples of suitable nitrogen-functional organosiloxanes are disclosed in U.S. Pat. Nos. 5,540,952 and 5,663,222, which are herein incorporated by reference. In general, any nitrogen-functional organopolysiloxane useful to impart fabric softness may be used in the present invention.
Most blends of polyisobutylenes and nitrogen-functional organopolysiloxanes are incompatible and phase separate upon standing into distinct liquid phases. The denser organopolysiloxane-rich phase is on the bottom and the less dense polyisobutylene-rich phase is on top. A distinct line of separation is observable. The separation may take several days to form. Centrifuging the composition can accelerate the formation of the separate phases. Separated blends create difficulties for end users. For example, if separation takes place in the storage tank containing the blend, the emulsion made therefrom could contain only one of the components. For instance, in the preparation of aqueous emulsions from concentrate, if the tank emptied from the bottom, the silicone-rich phase would be emulsified first. Emulsions made from the silicone-rich phase and applied to a textile substrate would have more yellowing than an emulsion prepared from a homogeneous, stabilized blend. Subsequent emulsions prepared from the isobutylene-rich phase would not provide adequate textile treating properties.
It has been found that a blend-stabilizing compound can be added to the incompatible concentrates to make the compositions stable even upon centrifugation. A blend-stabilizing compound is soluble in both the polyisobutylene and nitrogen-functional organopolysiloxane components, and prevents the polyisobutylene and nitrogen-functional organopolysiloxanes from separating. These stabilized concentrates may then be emulsified before treating a textile substrate by using suitable surfactants.
The polyisobutylene component of the subject invention is a polyisobutylene polymer, as defined herein, which may be soluble in the amino-functional organopolysiloxane, but is preferably dispersible therewith, within the range of concentration desired to be used; i.e., preferably in a range of polyisobutylene: amino-functional organopolysiloxane of about 95:5 to about 5:95, more preferably 95:5 to 30:70. The polyisobutylenes suitable are oligomeric polymers, copolymers, terpolymers and the like containing greater than 80 mol percent of hydrocarbon residues derived from unsaturated alkenes and/or cycloalkenes, a substantial portion of which are isobutylene residues. Generally, from about 60 mol percent to about 80 mol percent of the polyisobutylene polymers comprise isobutylene residues or the residues of mixtures of isobutylene and butylene. The polyisobutylene polymers may also comprise minor amounts of residues of unsaturated cycloaliphatic hydrocarbons such as cyclohexene, may contain residues of multiply unsaturated hydrocarbons such as butadiene, or other, singly unsaturated alkenes such as ethylene and propylene. Most preferably, greater than 80 mol percent and more preferably greater than 90 mol percent of polymer residues comprise butylene and isobutylene, i.e., the polymer is essentially an isobutylene homopolymer or isobutylene/butylene copolymer.
The polyisobutylene polymers may also contain functional groups such as anhydride groups or dicarboxylic groups such as may be derived by copolymerizing maleic anhydride optionally followed by hydrolysis. Epoxy-functional polyisobutylenes are also suitable. Epoxy-functional polyisobutylene polymers are available as Actipol™ polyisobutylenes from the AMOCO Corporation. Preferred polyisobutylenes are non-functional oligomeric polymers, copolymers, and terpolymers of mixtures of isobutylene, butylene, and butadiene. Such polyisobutylenes are available from the Amoco Corporation under the tradenames Indapol™ and Panalane™ polybutenes. Most preferably, the polyisobutylenes are hydrogenated wholly or partially to remove a substantial amount of residual unreacted double bonds. Such hydrogenated polyisobutylenes are available under the tradename Panalane™ as well. Particularly preferred are the partially hydrogenated polyisobutylenes sold as Panalane™ L-14E or L-14H. However, other polybutenes such as Indapol™ or Panalane™ L-10, L-50, L-65, L-100, H-15, H-25, H-35, H-40, H-50, H-100, H-300, H-1500, and H-1900 are also suitable.
The molecular weights of the polyisobutylene oligomers may preferably range from somewhat lower than about 250 to about 3000 Daltons (Da), preferably from about 300 to 1200 Da. These molecular weights are number average molecular weights. Polyisobutylenes having peak molecular weights in the range of less than 300 Da to about 3000 Da as determined by gel permeation chromatography are also suitable. Polyisobutylenes of higher molecular weights are also suitable, particularly when used as mixtures with lower molecular weight polyisobutylenes. When single polyisobutylene products are used, it is preferred that their number average molecular weights range from less than about 250 to about 2500 Da, more preferably 300 to 1000 Da, and most preferably 300 to 800 Da.
The fabric softening compositions of the subject invention may contain organopolysiloxanes which do not contain nitrogen-functional groups. Such non-nitrogen-functional organopolysiloxanes should be used in a minor amount relative to the total organopolysiloxane component. By "minor amount" as used herein is meant less than 50 percent in a weight basis unless indicated otherwise. Similarly, the term "major amount" indicates 50 percent by weight or more. Examples of non-nitrogen-functional organopolysiloxanes include polydimethylsiloxanes which may be trimethylsilyl capped, or which may bear alkoxy or hydroxyl groups at their termini or along the organopolysiloxane chain. Non-nitrogen-functional organopolysiloxanes are preferably α,ω-dihydroxypolydimethylsiloxanes. Preferably, such non-nitrogen-functional organopolysiloxanes comprise no more than 20 weight percent of the total organopolysiloxane component, more preferably no more than 10 weight percent. Most preferably, only nitrogen-functional organopolysiloxanes are used.
The hydrocarbon component of the fabric treating compositions of the present invention may contain hydrocarbon polymers other than polyisobutylenes as well. Examples include, but are not limited, to dispersible polyethylene, polypropylene, and other polyalkylene polymers and copolymers. By the term "polyalkylene" as used herein is meant polymers whose repeating units comprise one or more of the C2-12 lower alkenes or cycloalkenes for example, ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 2-hexene, 1-octene, cyclohexene, cyclooctene, cyclododecene, and the like, but contain less than a substantial portion, i.e., less than about 60 mol percent of 1-butene, 2-butene, and isobutene residues, or, in other words, are not polyisobutylenes as these latter polymers have been defined herein. Preferably, these polyalkylene polymers are homopolymers or copolymers of ethylene and propylene. Amounts employed are such that the polyalkylene polymers are stably dispersible in the composition, preferably less than 5 weight percent based on total composition weight, and most preferably about 1 weight percent or less. Polyalkylene copolymers containing dispersing-aiding groups such as carboxylic acid groups derived from acrylic acid and like compounds, optionally neutralized to augment dispersibility, are also useful.
The aqueous fabric treating compositions also generally contain an effective emulsifying amount of one or more surfactants. The emulsifying surfactant may be anionic, cationic, amphoteric, or non-ionic. Suitable surfactants include the various sulfonate and phosphonate surfactants such as alkylbenzenesulfonates and the like. Preferred surfactants are nonionic polyoxyalkylene surfactants such as polyoxyethylated alkylphenols and aliphatic alcohols, for example, polyoxyethylated nonylphenols and polyoxyethylated alkanols such as 1-butanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, and the like. Such surfactants are readily commercially available. Preferred emulsifying surfactants are the Genapol� surfactants obtained by polyoxyethylating one or a mixture of fatty alcohols, preferably Genapol� UD nonionic surfactants available from Hoechst-Celanese, most preferably Genapol� UD 30 and Genapol� UD 50. The surfactants chosen are those which provide a stable or readily redispersible emulsion, more preferably those which form a microemulsion with dispersed phase droplet size of less than 200 nm, preferably about 100 nm or less.
The aqueous fabric treating compositions also may contain other additives known to those skilled in the art, for example, antistatic agents, microbicides, and the like. Suitable microbicides, which may be present in effective amounts, for example, in the range of 0.01 weight percent to 0.2 weight percent, preferably about 0.05 weight percent, are quaternary nitrogen compounds such as dimethylbenzylammonium chloride, available from the H&S Chemicals Division of Huntington, Huntington, Ind., as FMB 50-5 Quat.
The fabric softening compositions may be supplied in numerous forms tailored to the end use desired and to specific customer requirements. For example, the compositions may be supplied as a concentrate containing only the organopolysiloxane component and the polyisobutylene component in the desired ratio, which may range from (organopolysiloxane:polyisobutylene) 5:95 to about 95:5, preferably 30:70 to 70:30, and more preferably about 40:60 to 60:40. When larger amounts of polyisobutylene are used, the degree of fabric softening may decrease to unacceptable levels. If too little polyisobutylene is used, the increase in resistance to yellowing will not be observed and the cost advantage to use of polyisobutylenes will be lost. Suitable concentrates preferably contain nitrogen-functional organopolysiloxanes other than aminoalkyl terminated organopolysiloxanes. Most preferably, such concentrates contain organopolysiloxanes with terminal, nitrogen-functional, but non-amino-functional groups, or pendant nitrogen-functional groups, most preferably pendant aminoalkyl groups as previously disclosed.
Such concentrates require addition of one or more emulsifying surfactants upon blending into an aqueous softening composition. The emulsifying surfactants or "dispersants" may be added to the siloxane/polyisobutylene concentrate prior to dispersing in water, or may be added to the water. Emulsions are prepared in conventional mixers, e.g., a Cowles mixer such as the Cowles Dispersator™ or Ross VersaMix PVM™ mixer. Other high shear mixers may be used as well. In some cases, easily-emulsifying or self-emulsifying blends may be made by employing suitable surfactants. In such cases, emulsions may be formed by simple, nonhigh shear mixing.
A fabric softener concentrate may be formulated and be emulsified just prior to use. A stable blend of nitrogen-functional organopolysiloxane and polyisobutylene may be made by combining the polysiloxane, polyisobutylene, and a blend-stabilizing compound, and/or suitable solubilizing agent such as D4 cyclic siloxanes or monobutylether cosolvents. The concentrate containing the blend-stabilizing compound is preferably a stable concentrate dispersion which does not separate upon standing for several weeks or longer. In some instances, for example, those compositions containing less than about 30 weight percent nitrogen-functional organopolysiloxane and particularly those compositions containing low molecular weight polyisobutylene oligomers, concentrates which appear to be true solutions may be obtained. The concentrates may also be formulated with desired amounts of microbicides, antistats, UV absorbers, and the like.
A preferred fabric treating concentrate contains 90 weight percent or more of a 65:35 to 35:65 blend of amino-functional organopolysiloxane and polyisobutylene, and a blend-stabilizing amount of a blend stabilizing compound which may be, without limitation, a surfactant, preferably from about 1.5 to 50 weight percent, more preferably about 15 weight percent of Tergitol� TMN3. By the term "blend stabilizing compound and like terms is meant a compound or blend of compounds which are effective to provide a stable dispersion or solution of nitrogen-functional organopolysiloxane and polyisobutylene in substantially non-aqueous form. The "blend stabilizing compound" may also be of assistance in emulsifying the composition in water, but this is not necessary to the function of the blend stabilizing compound. A concentrate may advantageously comprise 40 weight percent or more of the amino-functional organopolysiloxane and polyisobutylene components.
Rather than prepare a concentrate, the ingredients may be emulsified directly in water. The emulsified composition may be supplied as an aqueous dispersion suitable for end use directly for textile treating, or may be supplied as a concentrated aqueous dispersion suitable for dilution with water and optionally additional ingredients, co-solvents, etc., for use in more dilute form. When the end use composition is desired to be a microemulsion, an acid may be added in minor amount. Both inorganic acids as well as organic acids are useful, particularly organic carboxylic acids such as acetic acid, formic acid, and propionic acid. Microemulsion formation is promoted generally with the aid of a most minor portion of acetic acid. Amounts of glacial acetic acid useful range from about 0.01 weight percent to about 2 weight percent or more, preferably from about 0.06 weight percent to about 1.0 weight percent, more preferably about 0.06 weight percent to about 0.10 weight percent, these weight percents relative to the total weight of the aqueous composition. Other acids are useful in equivalent amounts. Most preferably, the aqueous composition contains from about 10 weight percent to about 50 weight percent, more preferably 10 to about 40 weight percent of the organopolysiloxane/hydrocarbon polymer mixture, this mixture containing nitrogen-functional organopolysiloxane and polyisobutylene in a weight ratio of from 5:95 to 95:5, more preferably 30:70 to 70:30, yet more preferably 40:60 to 60:40, and most preferably about 50:50. Suitable aqueous compositions may advantageously contain from 3 weight percent to about 20 weight percent each of the amino-functional organopolysiloxane component and the polyisobutylene component.
The fabric treating composition of the subject invention may be applied to any textile fiber compositions in need thereof. In general, such compositions comprise woven and knitted textile fabrics including but not limited to denims, worsteds, gabardines, jacquards, and other traditional woven materials. However, the fabric treating compositions may also be applied to textile compositions such as polyester fiberfill and like bulk products which require treating. All these are included within the term "textile fabric" as that term is used herein.
Non-limiting examples of aqueous fabric treating compositions may contain the following ingredients:
______________________________________Ingredient Weight Percent______________________________________Genapol UD 30 3.0Genapol UD 50 3.0Acetic acid, glacial 0.06-1.0Amino-functional 5-18OrganopolysiloxanePolyisobutylene 5-18Water 58-83Dimethybenzylammonium 0.05Chloride______________________________________
Water is preferably deionized water prepared by ion exchange treatment or reverse osmosis.
Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified.
A fabric treating concentrate is prepared by stirring together 40 parts Panalane™ L14E; 60 parts of an amino-functional organopolysiloxane available from Wacker Silicones, Adrian, MI under the product designation VP1434E; and 15 parts Tergitol� TMN3 surfactant. The blend is stable and does not separate upon standing or centrifugation.
An aqueous fabric treating composition is prepared by stirring together the following, in the order indicated:
______________________________________Ingredient Amount (Parts)______________________________________Genapol UD 30 12Genapol UD 50 12Water 24Acetic acid, glacial 5Panalane L14E 30Amino-functional 30Organopolysiloxane1Water 291.5______________________________________ 1 Wacker Silicones VP1478 organopolysiloxane.
The composition forms a stable emulsion.
Microemulsions containing amino-functional organopolysiloxanes but without polyisobutylene are prepared with the following compositions:
______________________________________ Amount AmountIngredient (Parts) C1 (Parts) C2______________________________________VP-1478M 15 --Amino-functionalOrganopolysiloxaneVP-1434M -- 17Amino--functionalOrganopolysiloxaneGenapol UD 50 6 --Genapol XO 60 -- 9Genapol XO 30 -- 1Acetic acid, glacial 0.31 0.11Benzyltrimethyl- 0.05 --ammonium chlorideDodigen 226 -- 0.05Water 78.64 72.84______________________________________
An aqueous emulsion of 15 wt. % Panalane L14E polyisobutylene was prepared using 3 wt. % each of Genapol UD 30 and Genapol UD 50 surfactants (UD 30 3%, UD 50 3%).
A series of identical cloth samples of 100% cotton woven material were treated with the aqueous textile treating compositions of the subject invention; with aqueous compositions containing only the aminofunctional organopolysiloxane as the active ingredient; and with aqueous compositions containing only polyisobutylene. Add-on was approximately 1 weight percent solids (based on fabric weight). The softener baths were prepared by diluting 13.3 g of each treating composition to 200 g with water. The samples were presented to a panel of 19 people for hand evaluation. Members of the panel had varying degrees of experience in judging hand. Samples were presented in groups of three, two of the samples in each group being identical. Each member of the panel was asked to pick the two samples he or she judged to be the same in terms of hand, and to select the sample they preferred, again in terms of hand. The data obtained resulted in the following conclusions:
1. The hand of samples treated in accordance with the subject invention are preferable to those treated only with polyisobutylene (i.e., Comparative Example C3)
2. Blends of amino-functional organo-polysiloxane and polyisobutylene in ratios of 70:30 and 30:70 are indistinguishable. A 50:50 blend is distinguishable from the 30:70 and 70:30 blends and is somewhat superior.
3. Most panel members were unable to distinguish between the compositions of the subject invention and a composition containing only VP-1434 amino-functional organopolysiloxane (Comparative Example C2). Those who were able to distinguish the hand of fabrics treated with these compositions preferred the hand of the amino-functional organopolysiloxane/polyisobutylene blend.
4. When VP-1478 amino-functional organopolysiloxane was substituted for VP-1434 (Comparative Example C1), the panel was again, for the most part, incapable of distinguishing between the amino-functional organopolysiloxane/polyisobutylene blend and a composition containing no polyisobutylene.
The subject compositions were compared with similar compositions containing only amino-functional organopolysiloxane. Cured fabric samples treated with the subject composition were noticeably less yellow than the samples treated with amino-functional organopolysiloxane only.
The subject compositions also exhibited surprisingly superior washfastness. Samples treated with compositions by the procedures outlined in the preceding paragraphs were subjected to numerous wash/dry cycles. Following seven wash/dry cycles, the fabrics treated in accordance with the subject invention displayed hand which was imperceivable from the hand of fabrics treated with amino-functional organopolysiloxane only. In addition, the fabrics treated with only amino-functional organopolysiloxane had noticeably greater yellowness after several wash/dry cycles.
In the claims, the use of the adjectives "a" or "an" with respect to a component should be taken to mean "one or more" unless otherwise indicated. By the term "textile treating composition" is meant a composition which is applied to textiles to impart a desirable property or change in property thereof, by leaving a property changing-effective residue thereon. Non-limiting examples of such properties are handle, softness, drape, washfastness, and lubricity. The basic and necessary components of the subject invention may be used to the exclusion of any ingredient not indicated as necessary, whether such ingredient is identified or not.
Having now fully described the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein.
|Cited Patent
|Filing date
|Publication date
|Oct 22, 1979
|Jan 20, 1981
|Sws Silicones Corporation
|Silicone polyether copolymers
|Oct 1, 1985
|Apr 28, 1987
|General Electric Company
|Aminofunctional polysiloxanes
|Dec 14, 1990
|Aug 13, 1991
|Union Carbide Chemicals And Plastics Technology Corporation
|Emulsions containing modified aminoorganosiloxane impart reduced yellowing when used as fabric softeners
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|Dec 17, 1991
|Dow Corning Corporation
|Aqueous silane water repellent compositions
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|Ppg Industries, Inc.
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|Dow Corning Corporation
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|Dow Corning Corporation
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|Dow Corning Corporation
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|Dow Corning Corporation
|Epoxy-terminated polyisobutylene-polydimethylsiloxane compositions
|Jun 7, 1995
|Apr 16, 1996
|Dow Corning Corporation
|Method for treating plastic, leather or rubber substrates
|Oct 4, 1994
|May 7, 1996
|Dow Corning Corporation
|Method for treating plastic, leather or rubber substrates
|Apr 10, 1996
|May 13, 1997
|Dow Corning Incorporated
|Silicone-polybutylene blends
|Title not available
|Citing Patent
|Filing date
|Publication date
|May 15, 2000
|Jun 26, 2001
|Unilever Home & Personal Care Usa, Division Of Conopco, Inc.
|Fabric softening compositions containing emulsified silicone
|May 12, 2000
|Oct 16, 2001
|Unilever Home & Personal Care Usa, Divison Of Conopco, Inc.
|Method of stabilizing fabric softening compositions
|Feb 20, 2001
|Nov 18, 2003
|Crompton Corporation
|Organopolysiloxane composition, emulsion-forming concentrates and aqueous emulsions formed therefrom and use of the emulsions in the treatment of textiles
|Sep 20, 2000
|Sep 7, 2004
|The Procter & Gamble Company
|Method of orienting shoes in a washing machine and devices for aligning shoes in a washing machine
|Mar 24, 2003
|Oct 24, 2006
|Wacker Chemie Ag
|Cyclodextrin laundry detergent additive complexes and compositions containing same
|May 5, 2004
|May 27, 2008
|The Clorox Company
|Rheologically stabilized silicone dispersions comprising a polydimethylsiloxane mixture
|Jan 21, 2005
|Jun 10, 2008
|The Procter & Gamble Company
|Fabric care and perfume compositions and systems comprising cationic silicones and methods employing same
|May 1, 2012
|The Armor AII/STP Products Company
|Water-based silicone dispersion containing low level of silicone oils
|Mar 24, 2003
|Sep 30, 2004
|Wacker Biochem Corp.
|Cyclodextrin laundry detergent additive complexes and compositions containing same
|May 5, 2003
|Nov 11, 2004
|The Procter & Gamble Company
|Cationic silicone polymer-containing fibrous structures
|May 3, 2004
|Nov 25, 2004
|The Procter & Gamble Company
|Soft fibrous structure
|Jan 21, 2005
|Jul 28, 2005
|The Procter & Gamble Company
|Fabric care and perfume compositions and systems comprising cationic silicones and methods employing same
|May 5, 2004
|Nov 10, 2005
|Serobian Ashot K
|Rheologically stabilized silicone dispersions
|Jul 17, 2007
|Nov 29, 2007
|Serobian Ashot K
|Water-Based Silicone Dispersion Containing Low Level of Silicone Oils
|Jun 27, 2008
|Nov 11, 2010
|Lenzing Aktiengesellschaft
|Filling Fiber With Improved Opening Performance, Method For Its Production And Its Use
|Jun 15, 2010
|Dec 15, 2011
|Heinrich-Heine-Universit�t D�sseldorf
|Waschaktive Zusammensetzung
|Jun 15, 2011
|Dec 21, 2011
|Heinrich-Heine-Universit�t D�sseldorf
|Wash-activated compounds containing anionically modified cyclodextrine
|U.S. Classification
|510/466, 510/515, 510/475, 510/516
|International Classification
|Cooperative Classification
|European Classification
|Dec 23, 1997
Owner name: WACKER SILICONES CORPORATION, MICHIGAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HUNTER, SCOTT;MARTIN, EUGENE R.;REEL/FRAME:008945/0835;SIGNING DATES FROM 19971210 TO 19971211
|May 27, 1998
Owner name: KANSEI CORPORATION, JAPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:OKUDA, YORIHITO;MURAKAMI, TAKASHI;ONO, KAZUMI;REEL/FRAME:009224/0554;SIGNING DATES FROM 19980324 TO 19980410
|Jul 10, 2001
|Certificate of correction
|Dec 25, 2001
|Certificate of correction
|Jan 8, 2002
|Certificate of correction
|Mar 24, 2004
|Maintenance fee reminder mailed
|Sep 7, 2004
|Lapse for failure to pay maintenance fees
|Nov 2, 2004
|Expired due to failure to pay maintenance fee
Effective date: 20040905


text:
Customer Reviews
Read reviews for this product
Posted 2/11/2016 at 2:52 AM by Jennifer
Love it! Gonna buy another one for a gift. So cute
Sending the same ornament to different places? If you order more than one of an item and want them shipped to different addresses, please order them individually. We will ask you for the individual shipping addresses later in the ordering process.
Sweet Pea Christmas Ornament
Personalized Christmas Ornament
SWEET PEA is permanently on this ornament. Many people call their babies or significant other sweet pea. What a fun gift to give them reminding them how special they are to you. This personalized sweet pea ornament is the cutest newborn baby gift or baby shower gift who can't wait for their precious bundle to arrive. We can personalize this peapod ornament with a name. Makes a great keepsake for a baby who wore a peapod costume for his or her first Halloween.
Material: Resin
Ornaments shown on our site are personalized, as examples only, so you can see where we put the words/names you give us. Some ornaments allow you to select hair or uniform color. If there is no color choice, it is not available on that particular ornament. We will do everything possible to catch any mistakes in spelling, etc., but are not responsible if we do as you request, and it is then not correct. The ornament you see above is the way it will look when you get it, except for the personalizing instructions you give us and any optional attributes you select.
Read what our customers say about our Personalized Christmas Ornaments and their shopping experience!Hover over testimonials to stop scrolling
11/30/2015 - "I ORDER ORNAMENTS EVERY CHRISTMAS. THIS IS MY FIFTH ORDER. John C."
8/29/2015 - "I have always been pleased with the high quality work done. In the few times there was a problem, it was rectified quickly and without any hassle. Arlene F."
12/30/2015 - "These ornaments are wonderful including the personalization! Ann L."
8/31/2015 - "Love the selection of ornaments. I was able to buy my family yearly ornaments all in one place. Renee Y."
12/9/2015 - "I liked the personalized ornaments options, my kids receive a Christmas ornament every year and I try to give them something that their interests are that year, this year I had a freshman going off to college so she received ornament with her college name and my freshman HS son received a football ornament with his HS name and football #, and each has the current year. It's great to have memories and ornaments they can keep for years to come. Traci H."
8/11/2015 - "I appreciate the vast variety of ornaments for personalization. I can always find one that is special for each grandchild. This has been a custom since at least 2009. What I miss is the opportunity to add, "Merry Christmas, Grandpa and Grandma G." I remember doing that in the beginning years. Joan G."
8/28/2015 - "I have orderd from the ornament shop for the last 5 years at Christmas time. I have always been happy with the product. Anonymous Respondent"
4/10/2016 - "Dear Dianne Absolutely first rate customer service! All five ornaments arrived, packaged extremely well, much faster than I could have imagined, taking the time into consideration of personalizing each ornament. I buy ornaments every Xmas for my 8 grandchildren. Some of them have 26 ornaments (one for each year of life)?? I have purchased some very expensive ornaments in the past years, especially for my older grandchildren. I am soooo pleased with your ornaments, at a much lower price than I have paid previously. I will be online again next year Sincerely, Agnes B."
12/6/2015 - "I'm pleased with the quality of the personalized ornaments for my 4 grandchildren. Would recommend this vendor. Helen H."
12/1/2015 - "Hi Debbie - I just wanted to personally thank you for the help with personalizing my order. I received my ornaments today, they are all perfect, but I am especially thankful for my little football player that you took the extra time and went the extra mile to make perfect just for me. I absolutely love it and I know Ryan will too! You have a life long customer in me! Thank you again soooo much, enjoy your holidays! Tammy T."

subset: commoncrawl


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AllianceHealth Oklahoma- Non-Invasive Cardiologist needed in Northwestern OK
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Non-Invasive Cardiology Opporutnity in Springdale, AR
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text:
Well met at Audiko, where you can easily aquire free ringtones for your cell phone. Today we have a ringtone of "Multiply" by Jamie Lidell as well as 106 other ringtones by Jamie Lidell. "Multiply" is a gorgeous track from the "Multiply" album that was composed by Jamie Lidell at their major label together with other 8 tracks. You can listen to all 8 Jamie Lidell – "Multiply" ringtone variations available here and download it for free just in a click. You can also search for other 5 albums produced by Jamie Lidell for all time. "Multiply" is referred to Soul, and you can download a huge amount of Soul artists absolutely for free. And finally, we have collected lyrics for this track and you can view it here as well. So feel free to browse, listen, download ringtones at Audiko.net. Make your phone sound cool!
Jamie Lidell Multiply Ringtone
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GREECE SITUATION UPDATES: The death of a 19-year-old Greek student has come to symbolize everything that's wrong with austerity!!!
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Anonymous Coward
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So, Germany doing military drills with Turkey today in the Aegean and both violated Greek airspace many times, Greek air-force intercepted them off course coz they didn't give any flight-plan whatsover, same with Pakistani and Turkish aircrafts yesterday. Thnx Germany, appreciated.
Any link on that?
Anonymous Coward 27412420
Yes it is on
link to www.defencenet.gr
But it is in Greek. The second article with the helicopter as a picture. But you have to google translate it as I cann't post a defencenet link from google translate
Anonymous Coward 27435174
Can you post the link to the article directly?? Now you just posted the link to the main website and I can't find the article you're talking about.
Anonymous Coward 27412420
Sorry I cannt cause it has Greek characters on the web address and whenever I post Greek letters GLP doesn't saw them. But below the big pictures there are 8 smaller ones. It is the 3 at the momment, the one with a helicopter.
Here is a google translation of the article, though
German violations of IDPs in the Aegean Sea in cooperation with the Turkish Navy
11/09/2012 - 21:00
Germany beyond dirty or "dishonest" - as most professing pro-government and pennies game-playing with the Memorandum and the country's debt and proceeded to brutal questioning the aerial challenge our borders in the Aegean with a German naval helicopter co LYNX.
This helicopter operating from the German Navy frigate which synaskeito with Turkish warships violated the National Aviation Area (ERA) and the rules of the Athens FIR in tandem with Turkish aircraft helicopters and fighter naval cooperation!
The German helicopter not only refused to hand over flight plans to Air Traffic Control Centre and in practice adopting the Turkish positions on the non-existence of Greek airspace between 6 and 10 nm proceeded to air "invasion."
More specifically, the Turkish and German aerial held today 11 breaches of Athens FIR and 2 violations of IDPs from a total of 18 aircraft of which: The 10 Turkish Air Force fighter, the Navy helicopters 5, 1 German helicopter and finally 2 the naval cooperation aircraft CN-235 of the Turkish Navy.
All the activity of these aeronautical ektylichthite forces in the northern and southeastern Aegean.
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Warning for young children, the elderly, and those with respiratory problems. 22 PA counties are under a Code Orange for May 25th.
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Erik the Juiceman
The story of a lazy kid and the people who live at his place. Sometimes stuff happens.
Have tea party and disco dance and sexy experiment!
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can you send a Zip file with all sounds to my e-mail adress???
i wanna have them!
Burnt Face Man rocks
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wow! oh you n00b! well its worth the tens i gave.
tres fun! like someone else said the sound was as crisp as a deep fried chip... Um I would have liked to have heard that James vanderwatsit say: "uuuur im not gay!" and maybe some narrator comments too. Cheers though it was ace.
I said it once, and I'll say it again.
This was great!
I love this =p
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New tests for LI students
Merryl Tisch, chancellor of the New York State Board of Regents, explains the goals of the Common Core Curriculum. Next week, students in grades three through eight will take standardized tests revised to reflect the new curriculum. Videojournalist: Sam Guzik (April 12, 2013)
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Breitling Jet Team demonstrates flight NBA star Tobias Harris visits Long Island schools Huntington death probed Cat revived at scene of Selden house fire Puppy of the Day: Paco High-end properties for sale on Long Island Red Cross campaigns for volunteers Fun facts about the Bethpage Air Show Cops: 2 killed in LIE crash LIRR holds public hearing on third track proposal LIRR president at third track hearing Puppy of the Day: Harley


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Group discussion topics on current affairs - GD Topics
Is personal grooming a necessity or just vanity?
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Should Hindi be the official language of India?
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India's huge population - bane or boon?
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India - really the NexGen superpower
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Ditching the Kyoto Protocol - Is India's objection on EU justified?
RE: Group discussion topics on current affairs - GD Topics yuvakshi grover (06-10-2014)
azng gd topics thankx for the guidance to the latest points really helpful
RE: Group discussion topics on current affairs - GD Topics Narender Sharma (07-4-2014)
I found your topics most helpfull
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Prime Mirren: A Recap/Review of "Prime Suspect: The Final Act"
PBS repeated the first part of the last installment of "Prime Suspect" tonight on Masterpiece Theatre. I never wrote a recap/review the first time it aired but in honor of its re-airing I decided to post one now.
You all know I'm a loyalist when it comes to American television drama: "Lost," "24," "Damages," "House," they're all among my favorites. But I've always been a sucker for British television drama, especially mysteries. And I don't mean the prissy, drawing room mysteries where all the characters sit around drinking sherry waiting for Miss Marple to blurt out, "It was Reginald in the pantry with an andiron."
I'm talking about spy shows like "MI-5," and crime shows like "Cracker," and "Touching Evil." Shows written and acted ruthlessly, rarely selling out a character or a plot line. The European locales are a welcome change from Hollywood back lots, and the often unfamiliar acting pool means you never know which red shirt won't be returning to the Enterprise. Anyone can be killed off at a moment's notice. So when a show like "Prime Suspect" starring the fabulous Helen Mirren returns for "The Final Act, "I'm there.
Read This Entire Post At Megan's Minute.


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The United States is deeply concerned about and closely monitoring developments in the Kyrgyz Republic and the affected border regions of Uzbekistan. The United States supports international efforts to facilitate peace and order and the provision of humanitarian assistance coordinated by the United Nations and the Organization for Security and Cooperation in Europe.
The United States intends to provide approximately $32 million to programs for humanitarian relief, reconstruction, and community stabilization.
These funds will be directed to meeting immediate humanitarian needs, providing assistance to displaced and returning families, and also to addressing the roots of the conflict through community development and conflict mitigation programs in the southern regions of the Kyrgyz Republic.
Assistance Committed to Date:
Additional USAID disaster expert staff is currently in Bishkek to work with U.N. agencies, NGOs, U.S. Government representatives, identify emergency humanitarian needs, and coordinate relief efforts in cooperation with the U.S. Embassy in Bishkek and U.S. Embassy in Tashkent.
Planned Assistance:
As soon as the security situation allows, the U.S. Government will begin deliveries of additional medical and other supplies donated by U.S. corporations and charities to the Kyrgyz Republic.
Secretary of Defense Gates has authorized the Department of Defense to support humanitarian assistance in the Kyrgyz Republic with the provision of medical and relief supplies and transportation of humanitarian relief personnel through the Manas Transit Center.
These commitments are in addition to the United States' ongoing annual assistance programs for the Kyrgyz Republic and Uzbekistan.


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DJ SANJ Raat Gayi Baat Gayi Remix and Promo
Pritish Nandy Communications' (PNC) latest outing "Raat Gayi Baat Gayi" has been nominated in two categories at the upcoming 16th Annual Star Screen Awards. The official promo for RGBG will the DJ SANJ remix of the title song. The film has been nominated in the Best Actor in a Supporting Role (Female) category for Neha Dhupia and in the Best Actor in a Comic Role category for Vinay Pathak. "This is a great honour for all of us at team PNC. 'Raat Gayi Baat Gayi' has got rave reviews from all corners and these nominations prove once again that content is the king in the business of cinema," Ram Kamal Mukherjee, vice president, PNC, said in a statement. Directed by Saurabh Shukla, it also stars Rajat Kapoor, Irawati Harshe, Anuradha Menon, Dalip Tahil, Navneet Nishan, Aamir Bashir and Sudhir Mishra.
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Port St. Lucie
Orchid Society
Some of our annual activities
Ok, title of the talk is "Growing an Orchid Collection for Quality and Awards". As far as a bio, I don't really have a prepared one. I've been growing orchids since I was 15. I have been a Judge with the AOS for 16 years. I currently have upwards of 80 awards. I am a hobby breeder focusing on quality and awards. I grow mainly Paphs, Catasetum types and Lycastes.
Ryan will be bringing plants for sale.


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Staff Picks
Nicole Richie's Incredible Top Knot & Fifi Awards Ensemble!YouTube 4y ago
Clueless Gamer: "Overwatch" With Peter Dinklage & Lena Headey - CONAN on TBSMashable 3h ago
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Nicole Richie's Incredible Top Knot & Fifi Awards Ensemble! http://bit.ly/SubClevverStyle - Subscribe to ClevverStyle! http://Facebook.com/ClevverStyle - Like Us! Our favorite fashion mentor, designer and beauty Nicole Richie steps out in a gorgeous gown at the 2012 Fifi Awards in New York City. Richie is a sight to see just about every time she steps out—whether that be in her own line or someone elses and for this big night, the lucky designer was Emilio Pucci. The frock from the designers Spring 2012 collection was absolutely stunning on the star with the trendy high low hemline. The detailing on the dress was unreal—with intricate embroidery and a light sequin detail. The sheer sleeves we're a great way to keep the dark hue summer appropriate and the neckline was the perfect sexy touch. The long train gave the dress an elegant feel even though the hemline was sky high in the front to show off Richie's lean legs. For shoes, Richie kept it all in the same color scheme going with some all black Brian Atwood pumps and she carried a simple clutch from her own line House of Harlow 1960. And in the jewelry department, Richie of course did it big with all bold pieces. She wore two statement rings and stunning drop earrings with a pewter and gold color combo. And Richie's hair was spot on—she loves the top knot, but she really glammed it up for this occasion giving it some extra detailing and height. She left her now signature bangs down and straight—which is a look I really love on Nicole. And for her makeup—she went dramatic much like the dress with a dark smokey eye that really stood out which she paired with just a light lip gloss. I'm Brianna Baxter for Red.


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Orient Kennels
1. Nancy's Kennel
9201 Boyd RdOrient, OH 43146
2. The Fur Seasons of Orient
13493 scioto darby rdorient, OH 43146
3. Darby Creek Kennels
Grove City, OH 43123
4. Concord Chapel Animal HospitalServices
Well, I can't speak for you since maybe they made a mistake. But the vets and staff have always been very accurate with diagnosing issues with my c…
5. Pet Buddies
Galloway, OH 43119
6. Angel Animal Hospital IncServices
175 Galloway RdGalloway, OH 43119
From Business: Personalized veterinary care for your dogs & cats located on a scenic property on Galloway Road. Room 3 available for large dog access. Private rainbow room availab…
7. Grove City Pet Pantry
3340 BroadwayGrove City, OH 43123
8. Dogs Rule
I have been taking my beagle mix pup to Dogs Rule for several months now and she loves it! They have a huge play area as well as several large fenc…
9. Fuzzz Playground
1620 Thrailkill RdGrove City, OH 43123
10. Alkire Kennels
We have been taking our dogs to Alkire Kennel for many years. Our previous dogs loved going to this kennel and our current dogs love it too. When …
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I have been vetting here for many years. Dr. Long is wonderful and the staff is very friendly and helpful. I recommend this place to everyone!
12. Lin Lar Pet Boutique
1096 Georgesville RdColumbus, OH 43228
From Business: The friendly staff at Lin Lar Grooming is always eager to help with any kind of grooming, bathing or boarding help you need. Owner Linda Kittle has been in business…
13. Georgesville Road Animal HospitalServices
I couldn't have found a better vet office for my cat.Everyone from the front desk to the vet was so caring and gentle.Every question I asked was ans…
14. Zoofari
I have been using Zoofari for years and my fluff comes home smelling and looking good. I have had no issues.
15. Fisher, Candace K
175 Galloway RdGalloway, OH 43119
16. Kountry Klipping LLC Pet Grooming
46 N London StMount Sterling, OH 43143
17. Healthy Pets Of WestgateServices
Healthy Pets of Westgate, and the branches in EMERGENCIES, has helped us with six cats (that FOUND US and we adopted)- most living to nearly 20 year…
18. Driving Park Animal Hospital
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19. West Jefferson Animal HospitalServices
121 E Main StWest Jefferson, OH 43162
From Business: If you live in West Jefferson or the surrounding area in Ohio, then you have picked the perfect site to find a veterinarian. Dr. Paul Stephenson, Dr. Tracy Arvin, a…
20. Buckeye Boarding
7885 Patterson RdHilliard, OH 43026
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21. Franklin, Tanya DVMServices
We started taking our pets to Dr. Tancred a few years ago. He is so passionate about animals and their well being. He always gives you the necessary…
22. Groveport Animal Clinic
6010 Groveport RdGroveport, OH 43125
From Business: Full Service Veterinary Clinic * Steven P. Tancred, D.V.M. * Tanya M. Franklin, D.V.M.
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855 E Livingston AveColumbus, OH 43205
From Business: AMENITY*Pet Health Insurance*Vet Store / Pharmacy*Pet Supplies*Pet Medical Library*Credit And Payment Options
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25. Ballou's North Star Pet Motel
Not fancy, but Ms. Ballou is freindly, she is reasonably priced and dependable. We've taken our dog's there several times and their first reaction …
26. The Doggy Den
1910 Memory LnColumbus, OH 43209
27. Bilek Boarding Kennel
25205 Chillicothe PikeWilliamsport, OH 43164
28. Critter SittersServices
5021 Singleton DrHilliard, OH 43026
29. Tail Wags Playground
1010 W 5th AveColumbus, OH 43212
30. Apollo's Warriors
4854 Vantage WayGroveport, OH 43125


text: Is a new sanctuary the last hope for the last of the Asiatic lion? Add to ... AP Video Published Monday, Jul. 09, 2012 12:54PM EDT Last updated Monday, Jul. 09, 2012 12:54PM EDT The world's last Asiatic lions may suffer under the tight grip of Gujarat, the Indian state that saved them. Conservationists hope India's Supreme Court will rule some of the animals should be sent to a new sanctuary in a neighboring state. Watch More Video: Trudeau plans day off in Japan to celebrate 11th anniversary Leaked recordings force Brazil minister out Obama interviewed by Anthony Bourdain in Vietnam Five dead in Hawaii skydiving plane crash 'No justice, no peace': People erupt in anger after officer acquitted in Freddie Gray case Daniel Craig speaks out against land mines at humanitarian summit John Kerry: U.S. drone strike killed Taliban leader Afghans confirm death of Taliban leader in U.S. drone strike Justin Trudeau to talk trade and investment in Japan Pope calls for action at Humanitarian Summit Obama arrives in Vietnam, seeks to turn old foe into new partner Manhunt underway after Massachusetts police officer killed Seven dead after Indonesian volcano erupts Sanders calls for path to citizenship for Mexicans Thousands march in Lima for LGBT rights Floods inundate Colombo, Sri Lanka Iraq says it retakes western town of Rutba from IS Russian paratroopers hold drills in central Ryazan region Single-seat solar plane lands in Ohio Kerry says Taliban leader was a 'continuing imminent threat' Comments AA


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Over The Door Jewelry Valet Storage Organizer Necklace Bracelets Rings Wall New
This item has been shown 0 times.
Over The Door Jewelry Valet Storage Organizer Necklace Bracelets Rings Wall New:
Over the Door Jewelry Valet
See all your jewelry at a glance for easy selection with this Over-the-Door Jewelry Valet. It holds over 300 pieces in a tangle-free fashion. Has places for rings, necklaces, earrings, bracelets, watches and more. The mesh screen can hold more than 75 pairs of earrings, or use it for pins and brooches. The 2 long hangers can be used for bracelets, watches or necklaces. Put your favorite necklaces or watches on the 2 revolving hangers at the bottom, each with 6 separate hooks. Store rings on the ring holders. Fits over most doors, or can be mounted on a wall. Easy assembly required. Mounting hardware included. Metal. 23-3/8" x 14" x 1-7/8".
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As if the debate on gay marriage was not provocative enough! This article by Patrick Dineen I commend because it will make both the left and the right squirm. It echoes the point I have been making, namely, that we lost the fight for traditional marriage fifty years ago with the introduction of no-fault divorce laws, but Dineen goes further and points to the ways the ambient culture can be conservative in ways that accelerate the decline of traditional marriage. Interesting stuff.
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Rancho Santa Margarita
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Medical assistant
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California State Physician Assistant License, issued by Physician Assistant Board under Medical Board of California....
Feb 17 - Long Beach, CA
Prior experience as nursing assistant preferred but not required. Be a part of the team leading the nation in healthcare....
Apr 28 - Fountain Valley, CA
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