text:
|Publication number
|Publication type
|Application number
|Publication date
|Feb 24, 1998
|Filing date
|Sep 19, 1996
|Priority date
|Sep 14, 1992
|Fee status
|Also published as
|Publication number
|Satish C. Sharma, John P. Kovalchin, Raymond J. Weinert
|Original Assignee
|Gencorp Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (15), Referenced by (40), Classifications (33), Legal Events (7)
|External Links: USPTO, USPTO Assignment, Espacenet
This is a division of prior application Ser. No. 08/212,619, filed Mar. 11, 1994, now U.S. Pat. No. 5,594,061 which is a continuation-in-part of application Ser. No. 07/944,585, filed Sep. 14, 1992, now abandoned.
The invention relates to an aqueous crosslinkable acrylic polymer coating composition which has a very low volatile organic compound content, and which upon application to a substrate and subsequent drying and curing forms a protective, stain resistant layer of a laminate. The invention further relates to a vinyl chloride polymer laminate having a stain, solvent and abrasion resistant, protective layer formed from the aqueous coating composition, and to a process for making the same.
Flexible vinyl chloride polymer sheet materials are commonly used in a wide variety of decorative applications including wallcoverings, upholstery and decorative films. It is generally desirable that the exposed surface of the vinyl chloride polymer sheets be provided with a protective, stain-resistant layer which can be easily cleaned without excessive rubbing or excessive use of harsh cleaning solvents. The protective layer should preferably exhibit good abrasion and solvent resistance. The aqueous coating composition should have a long shelf-life and good colloidal stability. For applications wherein a low gloss coating is desired for aesthetic reasons, such as for upholstery, it is highly desirable that flatting agents such as silica are capable of being effectively dispersed or redispersed in the coating composition.
A compounded and plasticized vinyl chloride polymer laminate having an outer adherent and stain resistant layer comprising the crosslinked reaction product of a reactive polyester having free carboxylic acid groups and an alkylated benzoguanamine-, urea- or melamine-formaldehyde resin is disclosed in U.S. Pat. No. 4,603,074.
One shortcoming with the stain resistant layer disclosed by U.S. Pat. No. 4,603,074 is that it is produced by coating a vinyl chloride polymer substrate with a solvent based curable polyester resin system having a high volatile organic compound content (typically 50 percent or more). The volatile organic components of the solvent which are evaporated during drying and curing of the coating must be recovered in order to comply with government regulations relating to chemical emission standards. Because of the problems and expense of solvent recovery and the potential for inadvertent human exposure to solvent vapor, it is highly desirable to provide a curable coating composition having a low volatile organic compound content which upon application to a vinyl chloride polymer substrate and subsequent curing forms an adherent, stain resistant layer of a laminate.
Another disadvantage with the stain resistant layer disclosed by U.S. Pat. No. 4,603,074 is that the ball point and felt tip pen stains cannot be easily removed with ordinary soaps or detergents, but instead often require harsher solvents such as acetone. It is desirable to provide a coating capable of forming a stain resistant layer on a vinyl chloride polymer substrate wherein the removal of frequently encountered stains can be effected without resorting to acetone or other harsh solvents.
U.S. Pat. Nos. 3,996,177 to Ludwig, 4,524,173 to Rehfuss et al., and 4,794,136 to Touhsaent each teach crosslinkable acrylic latex compositions.
Ludwig discloses a latex coating composition for providing hardboard with a hard, water resistant, and chemical resistant coating. The reference teaches that a combination of melamine-formaldehyde and urea-formaldehyde crosslinking agents are needed to achieve good shelf stability and good water resistance. Ludwig is unconcerned with substantially eliminating volatile organic compounds and consistently teaches the addition of substantial amounts of isopropyl alcohol to the disclosed latex coating compositions. Ludwig is also unconcerned with providing polyvinyl chloride substrates with low gloss coatings.
Rehfuss et al. disclose coating compositions for rigid metal or plastic substrates which simultaneously exhibit improved hardness and impact resistance. Rehfuss et al. utilize predominantly nonionic surfactants to allow the use of substantial amounts of acid catalysts to bring the pH of the composition down to the range of 1.0-2.0. It is disclosed that the low pH is required for rapid, low temperature curing, but makes the composition disadvantageous for use with a full range of substrates, and is therefore preferably used as a topcoat of a two-coat system. Rehfuss et al. teach that the latex polymer must contain from about 4 to about 9 percent by weight of an amide functional monomer to provide stability with the nonionic surfactants which are used. Rehfuss et al. are also unconcerned with providing a low gloss coating for polyvinyl chloride substrates.
Touhsaent teaches an adhesive composition for bonding a polyolefin film to a polyvinylidene chloride film and is completely unconcerned with providing a low gloss topcoat for polyvinyl chloride substrates. Touhsaent specifically teaches the use of chain transfer agents during preparation of the latex polymer which leads to lower molecular weight acrylic polymers which are generally unsuitable as coatings for polyvinyl chloride substrates because of their poor chemical and solvent resistance.
In accordance with the present invention, a substrate is coated with a water based composition having a low volatile organic compound content and comprising a crosslinkable acrylic polymer aqueous latex and an amino resin, preferably a partially or fully alkylated amino resin, crosslinking agent, and then heated at a suitable temperature for a period of time sufficient to cure and dry the coating to form a stain resistant layer of a laminate structure. The coatings of the invention generally contain no or only incidental amounts of volatile organic compounds such as less than about 1 percent by weight. The stain resistant layer has good adhesion to, for example, a vinyl chloride polymer substrate, and good resistance to chemical attack by solvents such as isopropyl alcohol. The coating compositions can be used without flatting agents to achieve a high gloss finish. However, conventional flatting agents such as wax and silica are usually compounded with the coating composition to reduce gloss when a flat finish is desired. Low gloss finishes are usually preferred for aesthetic reasons, particularly for vinyl chloride wallcoverings and upholstery. It is well known that flatting agents generally reduce the stain cleanability of cured coatings which form a protective layer of a laminate. The coatings of the present invention provide good cleanability without the use of harsh solvents even when high amounts of flatting agents are present in the coating.
The compositions of the invention exhibit excellent stability with or without the use of urea-formaldehyde crosslinking agents, and with or without flatting agents.
In accordance with a preferred aspect of the invention, polyvinyl alcohol is added to the coating compositions of the invention to further improve shelf-stability, especially when a more reactive (i.e. partially alkylated) melamine-formaldehyde resin is used. The polyvinyl alcohol also unexpectedly reduces the gloss of the coating, and is believed to improve chemical (i.e. solvent) resistance, thereby improving stain cleanability.
In accordance with a further preferred aspect of the invention, it has been discovered that certain surfactants based on dialkyl esters of sulfosuccinic acid provide unexpected improvements in scrub resistance when used in the coating compositions.
A still further aspect of the invention which has been found to provide unexpected benefits relating to improved flatting agent dispersibility and redispersibility involves the use of polydimethysiloxanes.
In order to achieve higher molecular weight latex polymers, the latex compositions of the invention are preferably prepared without chain transfer agents. Compositions of the invention which are prepared without chain transfer agents have been found to exhibit better scrub resistance.
The coating compositions of the invention are preferably used with a vinyl chloride polymer substrate, but can be advantageously employed with other substrates, especially polymeric substrates such as nylon, polyester, cellulosic and acrylic substrates.
In accordance with a preferred embodiment of the invention, a vinyl chloride polymer is used to form the substrate to which a coating composition of the invention is applied and cured to form a laminate having a protective stain resistant layer. The vinyl chloride polymer can generally be any of the commercially available vinyl chloride polymers produced by the well known methods of suspension, bulk, emulsion, or solution polymerization. The vinyl chloride polymer is preferably a homopolyvinyl chloride, but a copolymer comprising a major amount by weight of vinyl chloride and a minor amount by weight of a copolymerizable monomer such as vinyl acetate, vinylidene chloride, maleic ester, and mixtures thereof can be used. Mixtures or blends of vinyl chloride polymers can also be used.
The coating composition of the invention is preferably used in association with vinyl chloride polymers which are compounded with conventional plasticizers. The amount of plasticizer used to plasticize the vinyl chloride polymer to make it flexible may vary such as from about 30 to about 100 parts by weight per 100 parts by weight of total vinyl chloride polymer resin. Examples of plasticizers which may be used are butyl octyl phthalate, dioctyl phthalate, hexyl decyl phthalate, dihexyl phthalate, diisooctyl phthalate, dicapryl phthalate, di-n-hexyl azelate, diisononyl phthalate, dioctyl adipate, dioctyl sebacate, trioctyl trimellitate, triisooctyl trimellitate, triisononyl trimellitate, isodecyl diphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, polymeric plasticizers such as adipic acid polyester, azelaic acid polyester and sebacic acid polyester, epoxidized soybean oil, octyl epoxy tallate, isooctyl epoxy tallate, and mixtures thereof.
Other compounding ingredients are desirably incorporated in the vinyl chloride polymer compositions. Examples of such ingredients are the silicas such as precipitated silica, fumed colloidal silica, calcium silicate and the like, calcium carbonate, ultra violet light absorbers, fungicides, carbon black, barytes, barium-cadmium-zinc stabilizers, barium-cadmium stabilizers, tin stabilizers, dibasic lead phosphite, antimony oxide, zinc borate, molybdates and so forth and mixtures of the same. Titanium oxide, red iron oxide, phthalocyanine blue or green or other color pigments or dyes can be used. The pigments, dyes and other dry additives preferably are dispersed or dissolved in one or more plasticizers before being added to the plasticized vinyl chloride polymer compositions. These compounding ingredients are used in effective amounts by weight to control color, mildew, stabilization, viscosity and so forth of the plasticized vinyl chloride polymer.
The vinyl chloride polymer composition may contain suitable blowing or foaming agents such as sodium bicarbonate, and organic agents like 1,1'-azobisformamide, 4,4'-oxybis(benzenesulfonylhydrazide), p-toluenesulfonyl hydrazide and so forth to form a cellular or foamed vinyl chloride polymer composition layer or sheet on fusing. The blowing agents may require an activator.
Vinyl chloride polymer blending or extender resins, also, can be used in the compositions in a minor amount by weight as compared to the vinyl chloride polymer composition.
The ingredients forming the vinyl chloride polymer composition may be charged to and mixed together in any one of several mixing devices such as a Ross Planetary mixer, Hobart dough type mixer, Banbury, 2-roll rubber mill, Nauta mixer and ribbon blender and so forth.
The vinyl chloride polymer composition can be formed into layers or films which can be unsupported or supported (preferred). Where a vinyl chloride polymer plastisol composition is used, it may be cast on a release surface and heated to fuse it to form a film. Where a plasticized suspension grade vinyl chloride polymer composition is used, it can be calendered or extruded and fused to form a film. Temperatures may vary from about 200� to 400� F. However, it is preferred that in either case the compounded vinyl chloride polymer compositions be supported or have a backing. In the case of the supported vinyl chloride polymer composition, the backing can be a woven fabric (drill, scrim, cheesecloth, and so forth), a knit fabric, a nonwoven fabric, paper, etc. The fabric can be made of cotton, cellulose, nylon, polyester, aramid, rayon, acrylic or glass fibers or cords or mixtures of the same. It may be necessary in some instances to treat the fabric with an adhesive coating or dip to adhere or to adhere better to the vinyl chloride polymer composition.
The surface of the vinyl chloride polymer composition film or layer, supported or unsupported, is preferably printed with a suitable vinyl chloride polymer receptive ink to form desirable and novel patterns and designs. Such inks are well known and can be applied by various methods of printing such as by gravure, flexography, screen printing, jet printing, web printing and so forth. See "Modern Plastics Encyclopedia 1980-1981," pages 464-465. The printing operation may be repeated for up to five times or more to vary the colors and designs at temperatures of from about 150� to 165� F. for each printing step.
The vinyl chloride polymer substrate, supported or unsupported, printed or unprinted is preferably embossed to texture the vinyl chloride layer to provide a pattern or design for aesthetic or functional purposes. Embossing of thermoplastic films, layers or sheets is well known and is usually carried out by passing the film between an embossing roll and a backup roll under controlled preheating and post cooling conditions. See "Modern Plastics Encyclopedia 1980-1981," pages 454-455. Additional decorating or printing can sometimes be done with the above stated inks over the embossed vinyl chloride polymer surface for aesthetic purposes. The other polymeric substrates may be similarly processed as appropriate.
The aqueous based polymer coating for use as the outer or top coating for various substrates, especially on a vinyl chloride polymer substrate, is prepared by mixing a crosslinkable acrylic polymer aqueous latex with an amino resin, preferably an alkylated amino resin crosslinking agent, and a suitable crosslinking catalyst. The coating is applied to the substrate and cured at a temperature of from between about 150� F. and 320� F. and preferably from about 200� F. to about 280� F. to cause curing or crosslinking of the acrylic polymer and the amino resin. The coating may be applied directly to the vinyl chloride polymer substrate, with or without backing, with or without printing and with or without embossing.
The crosslinkable acrylic polymer aqueous latex is desirably prepared using conventional emulsion polymerization techniques which are well known in the art and well documented in the literature. Generally, any conventional anionic or nonionic emulsifiers known to the art and to the literature can be utilized in the emulsion polymerization. Suitable emulsifiers are set forth in McCutcheon's "Detergents and Emulsifiers," 1978, North American Edition, Published by McCutcheon's Division, MC Publishing Corporation, Glen Rock, N. J. Specific examples of conventional anionic emulsifiers which can be utilized include sodium alkyl sulfate, wherein the alkyl has from about 8 to about 22 carbon atoms such as sodium lauryl sulfate, sodium stearyl sulfate, various sodium alkyl benzene sulfonates wherein the alkyl has from about 8 to about 22 carbon atoms such as sodium dodecyl benzene sulfonate. Phenyl type phosphates, sulfosuccinates and disulfonated alkyl benzene derivatives having a total of from 8 to 22 carbon atoms, various fatty acid salts having from 12 to 22 carbon atoms, and various rosin acid salts can also be utilized. The amount of emulsifiers used is generally from about 1 to about 6 parts by weight per 100 parts by weight of monomer. Examples of nonionic emulsifiers include alkylaryl polyester alcohols, block copolymers of ethylene oxide and propylene oxide, and polyalkylene glycol ether. Seeding techniques can be used, as desired to achieve more uniform latex polymer particle sizes, but are not generally necessary.
Desirably, the monomer or comonomer composition utilized in the polymerization of the acrylic polymer includes at least one monomer free of both carboxylic acid functionality and hydroxyalkyl ester functionality and having a carbon-carbon double bond. Preferably, the majority of monomers by weight utilized in the polymerization of the acrylic polymer are alkyl acrylates or alkyl methacrylates with the alkyl portion having from 1 to about 16 carbon atoms and preferably from 1 to about 10 carbon atoms. Vinyl substituted aromatics having from about 8 to about 12 carbon atoms can also be utilized in the acrylic polymer in minor amounts. Examples of acrylates and methacrylates include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, stearyl acrylate, lauryl acrylate, methylmethacrylate, t-butylmethacrylate, propylmethacrylate, and the like, with mixtures of methylmethacrylate and 2-ethylhexyl acrylate being preferred. Examples of vinyl substituted aromatics which may be used include styrene, alpha-methylstyrene, and the like.
Small amounts of multifunctional acrylate monomers containing two or more carbon-carbon double bonds including diacrylate and triacrylate monomers such as ethylene glycol dimethacrylate, diethylene glycol diacrylate and trimethylolpropane triacrylate may also be used in the polymerization of the acrylic polymer to create branched polymers. Various vinyl compounds such as divinyl benzene can also be used. The amount of optional multifunctional acrylate which can be utilized is generally in the range from about 0.005 to 10 parts by weight per 100 parts by weight of total monomer.
To impart crosslinkability to the acrylic polymer, effective amounts of crosslinkable comonomers having a carbon-carbon double bond and containing carboxylic acid functionality, hydroxyalkyl ester functionality, or both carboxylic acid and hydroxyalkyl ester functionalities are utilized in the acrylic latex polymer. Examples of crosslinkable comonomers which may be used include unsaturated mono- or dicarboxylic acids containing from 3 to about 12 carbon atoms, hydroxyalkyl acrylates wherein the alkyl contains from 2 to about 6 carbon atoms, hydroxyalkyl methacrylates wherein the alkyl contains from 2 to about 6 carbon atoms, and hydroxyalkyl esters of unsaturated dicarboxylic acids, wherein the alkyl portion has from about 2 to about 6 carbon atoms and the ester has a total of from about 5 to about 18 carbon atoms. To achieve adequate shelf-stability, cure properties and coating properties, the acrylic latex compositions should generally contain from about 2 to about 9 or 10 weight percent hydroxyl functional monomers.
Examples of carboxylic acids containing comonomers include various mono- and di-carboxylic acids and anhydrides such as itaconic acid or anhydride, maleic acid or anhydride, fumaric acid, allyl acetic acid, acrylic acid and methacrylic acid. Comonomers having a hydroxy- alkyl ester functionality include hydroxyethyl acrylate and methacrylate, hydroxypropyl acrylate and methacrylate, and the like. Comonomers having both hydroxy- alkyl ester and carboxylic acid functionalities include the partial hydroxyalkyl esterification product of a dicarboxylic acid and a diol, such as the condensation product of fumaric acid or itaconic acid with a diol such as ethylene or propylene glycol. Acid monomers can be used in small amounts such as less than 4 or 5 weight percent and more preferably less than 1 or 2 weight percent to enhance shelf-stability, but are generally not desired or required. Various mixtures of monomers and crosslinkable comonomers can be utilized to produce the acrylic polymers used in the coating composition.
A particularly preferred latex polymer consists of from about from 2 to about 9 or 10 parts by weight of hydroxyethyl acrylate, from about 15 to 40 parts by weight of 2-ethylhexyl acrylate, and from about 50 to about 83 parts by weight of methyl methacrylate, such that the total of the monomers is 100 parts by weight.
The latex polymer compositions of the invention are preferably prepared without chain-transfer agents which are commonly used in many prior art latex compositions. It has been found that latex compositions of the invention exhibit substantially better scrub resistance when chain-transfer agents are not used.
The amino resins are well known to the art and well documented in the literature, as for example, in "Aminoplastics," Vale et al. Iliffe Books Ltd., London, 1964; "Amino Resins," Blair, Reinhold Publishing Corporation, New York, 1959; "Modern Plastics Encyclopedia of Polymer Science and Technology," John Wiley & Sons, Inc., Vol. 2, 1965, pages 1 to 94, all of which are hereby incorporated by reference.
Preferably, the amino resin crosslinking agent can be various amino-formaldehyde resins known to the literature and to the art such as an alkylated benzoguanamine-formaldehyde, an alkylated urea-formaldehyde or, more preferably, an alkylated melamine-formaldehyde resin. Mixtures of these resins can also be used. Other amino-formaldehyde resin crosslinking agents which may be utilized include alkylated dihydroxyethyleneureaformaldehyde, alkylated glycolurilformaldehyde, alkylated acetoguanamine-formaldehyde, alkylated aniline-formaldehyde, and the like. Effective amounts of the crosslinkable acrylic polymer and amino resin crosslinking agent are employed to provide a stain resistant, crosslinked layer having good durability and flexibility and having good adhesion to various substrates, such as vinyl chloride polymer substrate on curing and crosslinking. Generally, the amount of crosslinking agent used is in the range from about 1 to about 50 parts by weight per 100 parts by weight of the crosslinkable acrylic polymer on a dry basis. These materials are cured at a temperature of from between about 150� F. and 320� F. and preferably from about 200� F. to about 280� F. in the presence of an acidic crosslinking catalyst like boric acid, phosphoric acid, acid sulfates, hydrochlorides, phthalic anhydride or acid, oxalic acid or its ammonium salts, sodium or barium ethyl sulfates, aromatic sulfonic acids such as p-toluene sulfonic acid (preferred) and the like. The amount of crosslinking catalyst used is generally from about 1/2 part to about 10 parts by weight per 100 parts by weight of acrylic polymer on a dry basis. A preferred crosslinking resin which can be used either alone or in combination with other amino resin crosslinking agents to obtain a coating composition exhibiting good stain cleanability and shelf-stability is melamineformaldehyde resin. The latex compositions of the invention generally are adjusted and utilized at near neutral pH, such as from about 6 to 10, and more preferably from about 7-9. Accordingly, a predominance of non-ionic surfactants and the incorporation of amide functional monomers into the acrylic polymer, are not required as with the compositions of Rehfuss et al. Prior to curing, flatting agents or other conventional additives can be added in conventional amounts to the acrylic coating mixture.
In accordance with a preferred aspect of the invention, polyvinyl alcohol is included in the coating compositions of the invention to further improve shelf-stability and to reduce gloss. The addition of polyvinyl alcohol is also believed to improve abrasion resistance and solvent resistance. Suitable polyvinyl alcohols generally include any of various commercially available polymers having a weight average molecular weight of from about 20,000 to about 200,000 and more preferably from about 25,000 to about 35,000. Even relatively small amounts of polyvinyl alcohol (PVOH) have been found to reduce gloss and increase shelf-stability. However, PVOH is desirably used in an amount of from about 3 to about 50, more desirably from about 6 to about 50, and most preferably from about 10 or 12 to about 18 or 20 parts by weight per 100 parts by weight of the total weight (dry basis) of the acrylic latex polymer and the amino crosslinking agent or agents.
The compositions of the invention generally contain flatting agents to reduce the gloss of substrates which have been coated. Reduced gloss is aesthetically desired for most wallcoverings and upholstery applications. Conventional flatting agents such as silica and silicates are generally utilized in conventional amounts such as from 5 to 50, and more preferably from 10 to 30 parts by weight per 100 parts by weight of the total weight (dry basis) of the acrylic polymer and amino crosslinking agents. It has been discovered that the dispersibility and redispersibility (i.e. the ability to redisperse after settling) of flatting agents, particular silica flatting agents, can be dramatically and unexpectedly improved by adding polysiloxanes to the coating composition. Particularly preferred polysiloxanes include polyether and polyester modified polydimethylsiloxanes, and polyester modified hydroxyl functional polydimethylsiloxanes. The most preferred polysiloxane is aminoethylaminopropyldimethoxysilyl end-blocked polydimethylsiloxane. It is believed that the polydimethylsiloxane adsorbs on silica thereby stabilizing the silica dispersion by a steric stabilization mechanism. Polydimethysiloxanes which contain functionality (e.g. basic) that will adsorb strongly on the acidic silica are expected to be most efficient. Effective amounts of polydimethylsiloxane generally range from about 0.01 to about 25 parts by weight, and more desirably from about 0.1 to about 10 parts by weight, and most preferably from about 0.1 to about 5, per 100 parts by weight (dry basis) of acrylic polymer and crosslinking agent or agents. The most effective amounts depend on the particular polydimethylsiloxane being used and the amount of flatting agent added to the composition.
It is generally desirable to add surfactants to the coating composition to obtain good substrate wetting and uniform coating of the substrate. It has been discovered that unexpected improvements in solvent and scrub resistance are achieved when certain dialkyl esters of sulfosuccinic acid, wherein the alkyl group contains from about 6-30 carbon atoms, are added to the composition. A particular preferred surfactant is sodium bis(2-ethylhexyl) sulfosuccinate which is avail- able from Permuthane Corporation under the product designation "KM-10-1610."
It has been found that, in addition to providing for better solvent and scrub resistance, the dialkyl ester sulfosuccinic acid surfactants can be used in generally smaller amounts than other conventional surfactants. Suitable amounts of dialkyl ester sulfosuccinic acid surfactant range from about 0.5 to about 10 parts, and more preferably from about 1.0 to 5 parts by weight per 100 parts by weight of the total weight (dry basis) of the acrylic polymer and amino curing agent or agents.
The coating compositions of the invention are generally free of any intentionally added volatile organic compounds, preferably do not contain any or contain only incidental amounts of volatile organic compounds. The latex coating compositions of the invention typically contain less than about 1.0 percent volatile organic compounds by weight.
The stain resistant laminates of the present invention are particularly well suited for use as wallcoverings, tablecloths, shoe uppers, luggage exteriors, upholstery, vehicle interiors and seats, golf bags and other sporting goods.
A typical low gloss latex coating composition for use with polyvinyl chloride wallcoverings or upholstery is as follows:
______________________________________Formulation of Waterborne Acrylic CoatingComponent PHR Function______________________________________Acrylic Latex 90 CoatingMelamine 10 CrosslinkerPTSA 6.5 CatalystSilica 22.5 Flatting AgentDow Corning 478 1.3 StabilizerWetting Agent 1.6 Substrate WettingPVOH 10 Shelf Life, Solvent/Abrasion______________________________________
While the invention is primarily intended for use as a coating composition for vinyl chloride polymer sheet materials, it may also be advantageously used as a coating for various polymeric or cellulosic materials such as paper, fabrics made from synthetic or natural fibers, nylon, polyester or acrylic substrates.
The invention will be better understood by reference to the following examples.
Preparation of Latexes
The latexes (emulsion polymers) used were mostly prepared in quart size glass bottles using a batch-wise seeded emulsion polymerization process. The basic recipe and the polymerization procedures are given in Table I. The solids content of the latexes was in the 46-47% range. The pH of the "as prepared" latexes (i.e., before pH adjustment subsequent to polymerization) was in the 3-4 range.
TABLE I______________________________________Preparation of Seed LatexRecipe PartsIngredient Wet Dry______________________________________Deionized Water 88.5 --Dowfax 2A1.sup.(1) (10%) 3.6 0.36Sequestrene Na3 T.sup.(2) 0.075 0.075Styrene 6.0 6.00K2 S2 O8 0.15 0.15Deionized Water 15.00 --Total 113.325 6.585______________________________________ .sup.(1) Sodium dodecyl diphenylether disulfonate product of Dow Chemica Co.,; diluted to 10% active concentration. .sup.(2) Trisodium ethylenediamine tetraacetate trihydrateproduct of CibaGeigy. Chelating Agent.
The ingredients were mixed in the order given above, purged with nitrogen, and reacted at 65� C. for 2 hours. At the end of the reaction, the product was cooled to room temperature. No coagulum was formed and no filtering was necessary.
TABLE I (cont'd.)______________________________________Preparation of Final LatexRecipe PartsIngredient Wet Dry______________________________________Seed Latex 113.325 6.585Surfactant(s)* As neededMonomers* 94.0 94.0K2 S2 O8 0.2 0.2Deionized Water 10.0 --______________________________________ *The specifics of surfactants and monomers used in various experiments ar given in appropriate tables.
The ingredients were mixed in the order given above, purged with nitrogen, and reacted at 65� C. to >99% monomer conversion. At the end of the reaction, the product was cooled to room temperature and filtered through a fine paint filter to remove the coagulum.
Preparation of Coating
The pH of latex was adjusted to the desired level (7-9 pH units) with sodium hydroxide, triethanolamine, ammonium hydroxide, or sodium bicarbonate, before the addition of other ingredients such as the external crosslinking agent (e.g., Cymel 303--hexamethoxymethyl melamine; a product of American Cyanamid Co.), wax, and flatting agents. All ingredients were slowly added to the latex and mixed/dispersed well. Para-toluenesulfonic acid (catalyst) was diluted to 10 percent concentration in water, adjusted to a pH of 7.3-7.5, and added to the coating immediately prior to use.
Application of Coating
The substrates used in this work were plasticized polyvinyl chloride (PVC or vinyl) laminates like those described in the U.S. Pat. No. 4,603,074 but without the stain resistant coating of the above patent. An 81/2"�16" piece of the vinyl was taped to a flat glass plate maintained at 175�-185� F. using radiant heat. The coatings were applied to the substrates using a wire-wound rod (Meier Rod), allowed to dry under radiant heat for 1 minute, and then cooled to room temperature. The coatings were further cured in a forced air oven maintained at 250� F. Cure times were 1-3 minutes.
The coating thickness (calculated from coat weights) was in the 10-30 μm range.
Stain Resistance/Cleanability Testing
Samples were cut from the coated sheet, marked with the stain, and allowed to age for 10 minutes (for short-term stains) or for 16-24 hours (for long-term stains). The stain resistance or ease of cleanability of the coating was then tested first by wiping the stain with a dry paper tissue, spraying with the cleaning agent (e.g. 409 Household Cleaner, isopropanol) and wiping with a paper tissue, or spraying with the cleaning agent and hand scrubbing with a nylon bristle brush. A maximum of 50 double scrubs was tried.
Table II lists the ingredients (except deionized water) for a series of latexes that were prepared by varying the amount of surfactant (Aerosol OT). Details of the preparation procedures are given in Table I. The reaction time was 6 hours. Stable latexes were obtained. Even at the lowest level of surfactant used, the coagulum level was not excessive.
Each of the four latexes A-D was formulated into a coating containing (on dry parts basis) 18.75 parts of latex, 0.135 parts of KM-10-1610 wetting agent (an anionic surfactant obtained from Permuthane Coatings, Peabody, Mass.), sodium hydroxide to adjust pH to 8.3-8.4, and 2.1 parts Cymel 303. Cleanability (10 minute stain) results for these coatings are given in the bottom part of Table II. The data show that all of the coatings had excellent cleanability since both the ball point pen and the marker stains could be readily cleaned with a household cleaner and without the use of solvent. Furthermore, even repeated staining at the same spot did not affect the cleanability.
For the uncoated substrates, it was observed that the stain was very dark even after 50 scrubs with the 409 Household Cleaner.
TABLE II______________________________________ Latex:Ingredients + -A -B -C -D______________________________________Seed Latex 6.585 6.585 6.585 6.585Aerosol OT.sup.(1) 0.6 1.0 1.5 2.0Methyl methacrylate 62.0 62.0 62.0 62.02-Ethylhexyl acrylate 26.0 26.0 26.0 26.0Hydroxyethyl acrylate 6.0 6.0 6.0 6.0K2 S2 O8 0.2 0.2 0.2 0.2Latex Solids, % 46.3 46.3 46.3 46.5Coagulum.sup.(2) 0.48 0.03 0.03 0.01______________________________________Stain Resistance/Cleanability of Coatings Scrubs to Clean (409 Household Cleaner)Latex Stain Type 1st Stain 2nd Stain 3rd Stain______________________________________A Carter Marker 25 25 Not tested (Black)B Carter Marker 10 15 20 (Black)C Carter Marker 20 20 20 (Black)D Carter Marker 20 20 20 (Black)A Ball Point Pen Not tested (Bic, Black/Blue)B Ball Point Pen 3 3 3 (Bic, Black/Blue)C Ball Point Pen 3 3 3 (Bic, Black/Blue)D Ball Point Pen 3 3 3 (Bic, Black/Blue)______________________________________ + On dry parts basis. Rest was deionized water. .sup.(1) Dioctyl ester of sodium sulfosuccinic acid a product of America Cyanamid Co. .sup.(2) Part per hundred parts of monomers.
A 22 experimental design with center point was used to evaluate the effect of variation of latex polymer/Cymel 303 ratio and the catalyst concentration on the properties of the coatings. The latex used was identical to Latex B of Table II (Example 1). The coating compositions and the stain cleanability data are given in Table III. All of the coatings gave adequate cleanability and thus fall within the scope of the present invention. The surface of the coatings was unaffected by scrubbing.
The cleanability of the sample coated with Coating No. 6 (Table III) was checked again after 6 weeks storage in the laboratory. For the 10 minutes stains, both the ball point pen (black) and the Carter Marker (black) stains could be cleaned in 10 scrubs with the 409 Household Cleaner, and the lipstick stain could be wiped off with the paper tissue. To clean the overnight (16-20 hours) stains, it took 20 scrubs with 409 Cleaner for the ball point pen, 30 scrubs with isopropyl alcohol (IPA) for the Carter Marker, and 2 scrubs with IPA for the lipstick.
TABLE III______________________________________Effect of Latex/Cymel 303 Ratio and Catalyst LevelCoating Composition.sup.(1)Coating Cymel RelativeNo. Latex 303 Catalyst Stain Cleanability.sup.(2) Rating______________________________________1 17 3 0.2 Very light stain left 4 after 50 scrubs2 19 1 0.2 Stain barely visible 3 after 50 scrubs3 17 3 0.4 Stain barely visible 2 after 50 scrubs4 19 1 0.4 Stain barely visible 2 after 50 scrubs5 18 2 0.3 Stain barely visible 3 after 50 scrubs6 18 2 0.4 Stain gone after 1 (Best) 25 scrubs______________________________________ .sup.(1) Dry parts .sup.(2) Carter Marker (black) stain (10 minutes); 409 Household Cleaner.
Another latex (Latex E) was prepared following the same procedure and recipes as given earlier (Tables I and II) except that instead of Aerosol OT (Table II), 0.72 parts (dry basis) of KM-10-1610 wetting agent was used as the surfactant during the polymerization of the latex. Coatings were prepared from Latex E using the recipes given in Table IV. The stain cleanability results for these coatings are given in Table IV. The data indicate that any of the various bases may be used to adjust the pH of the latex without significantly affecting the stain cleanability.
TABLE IV______________________________________Coating No.: 7 8 9______________________________________Contents.sup.(1)Latex E 18 18 18Dowfax 2A1 0.1 0.1 0.1pH Adjustment.sup.(2) Triethanolamine Sodium Ammonium Hydroxide HydroxideCymel 303 2.0 2.0 2.0Catalyst 0.4 0.4 0.4StainCarter Marker 20 Scrubs with 40 Scrubs with >50 Scrubs with(10 Minutes) 409 Cleaner 409 Cleaner 409 CleanerLipstick Wipes clean with dry paper tissue(overnight)Ball Point Pen 50 Scrubs with 40 Scrubs with 60 Scrubs with(Overnight) 409 Cleaner 409 Cleaner 409 CleanerCarter Marker Stain washes off with IPA. No scrubbing needed.(Overnight)______________________________________
A latex (Latex F) was prepared with a recipe essentially identical to that for Latex E by using the following procedure. To a 5-gallon reactor vessel, 10712.53 gms of deionized water, 93.87 gms of a 45 percent solution of Dowfax 2A1, 8.8 gms of Sequestrene Na3 T, and 704.0 gms of styrene were added. The temperature was adjusted to 65� C. and a solution containing 17.60 gms of potassium persulfate and 1760 gms of deionized water was added to the reactor while stirring continuously. The reactor was purged with nitrogen and the reactants were allowed to react for 2 hours. The reactants were cooled to room temperature and dropped into a container through a filter. The monomer conversion was essentially 100 percent and no coagulum was formed during the preparation of this seed latex.
To a clean 5-gallon reactor, 5780.0 gms of the above seed latex and 136.0 gms of a 27 percent solution of KM-10-1610 wetting agent were added. Separately, a mixture (Mixture A) containing 3162 gms of methyl methacrylate, 1326 gms of 2-ethylhexyl acrylate, and 306 gms of hydroxyethyl acrylate was prepared and mixed well. Seven hundred and fourteen (714) gms of this mixture was added to the reactor which was maintained at 65� C. under a nitrogen blanket. A solution containing 10.2 gms of potassium persulfate and 510 gms of deionized water was then added to the reactor. The rest of Mixture A (4080 gms) was added to the reactor at a constant rate over a period of 3 hours. The reactants were allowed to react further for 2 more hours and then cooled to room temperature. Sixty-eight (68) gms of a 45 percent solution of Dowfax 2A1 was added to the reactor and mixed well. The monomer conversion was essentially 100 percent and only a trace of coagulum was formed. The number average particle diameter of the latex was determined (by Capillary Hydrodynamic Fractionation technique) to be ˜150 nm.
Coatings from Latex F were prepared according to the recipes given in Table V, applied to vinyl substrates and cured at 250� F. for 3 minutes. As might be expected, the coatings which contained microcrystalline wax and silica (Coatings 11-14) were less glossy and much duller than coating No. 10. The stain cleanability data are given in Table V. Cleanability worsens significantly with the addition of wax and silica to the coating. This is not unexpected. However, the stains are still cleanable without the use of acetone or other harsh solvents.
TABLE V______________________________________Coating No.: 10 11 12 13 14______________________________________Contents.sup.(1)Latex F.sup.(2) 18 18 16 16 14Jonwax 22.sup.(3) -- 1 1 1 1Syloid 820.sup.(4) -- 3.4 3.4 3.4 3.4Cymel 303 2 2 4 4 6Catalyst 0.4 0.6 0.4 0.6 0.4Stain CleanabilityStainCarter 30 Scrubs Not cleanable with 409 Household Cleaner.Marker with 409(Overnight) Cleaner OR 50 Scrubs 50 Scrubs 30 Scrubs 50 Scrubs Washes with IPA with IPA with IPA with IPA off with IPA (No Scrub- bing)Ball Point Not Done 50 Scrubs 40 Scrubs 50 Scrubs 30 ScrubsPen (Over- with IPA with IPA with IPA with IPAnight)Ball Point Not Done 30 Scrubs 30 Scrubs 20 Scrubs 20 ScrubsPen (10 with IPA with 409 with 409 with 409Minutes) Cleaner Cleaner Cleaner______________________________________ .sup.(1) All parts are on a dry basis .sup.(2) pH adjusted to ˜8 with triethanolamine. .sup.(3) Microcrystalline wax a product of S.C. Johnson Wax. .sup.(4) Silica Flatting Agent from Davison Chemical, W. R. Grace and Co.
Carboxylic acid functional monomers are sometimes polymerized with the other monomers to impart increased colloidal stability to the latexes. Latexes G and H were prepared to determine the effect of methacrylic acid monomer on stain cleanability of the coatings. Latexes were prepared with the recipes given in Table VI and using the procedure given in Table I.
Coatings were prepared from these latexes by mixing together (on dry basis) 18.75 parts of latex, 0.135 parts KM-10-1610, adjusting the pH to 8.3 with sodium hydroxide, and adding 2.1 parts Cymel 303, and 0.4 parts para-toluenesulfonic acid catalyst. The Carter Marker stains (10 minutes) for the coatings could be cleaned in 20-30 scrubs with 409 Cleaner, indicating that a small amount of carboxylic functional monomer (about 1 percent by weight) had no adverse effect on stain cleanability.
TABLE VI______________________________________Latex:Ingredients.sup.(1) G H______________________________________Seed Latex 6.585 6.585Aerosol OT 0.67 1.00Methyl methacrylate 61.0 62.0Methacrylic acid 1.0 --2-Ethylhexyl acrylate 26.0 26.0Hydroxyethyl acrylate 6.0 6.0K2 S2 O8 0.2 0.2Latex Solids, % 46.2 46.5Coagulum.sup.(2) 0.27 0.28______________________________________ .sup.(1) On dry parts basis. Remainder was deionized water. .sup.(2) Parts per 100 parts monomers.
This example illustrates the unexpected beneficial effects relating to dispersibility and redispersability of silica flatting agents in the coating when certain polydimethylsiloxanes (PDMS) are added to the composition. The most effective PDMS was found to be Dow Corning 478 Fluid (an aminoethylaminopropyi-dimethoxysilyl-end-blocked polydimethylsiloxane).
The latex used in this study was identical to Latex F (Example 4). All coatings contained (on a dry basis) 10.8 gm of latex, 1.2 gm of "Cymel 373" (a partially methylated melamine-formaldehyde resin from Cytec, formally American Cyanamid), 0.04 gm of "Drew L198" defoamer (a product of Drew Chemical Corporation), and 2.7 gm of "Syloid 820" silica flatting agent (a product of W.R. Grace and Co.). The total solids content for each of the coating compositions (6-1 through 6-5) was about 34 percent. The effect of the addition of varying levels of Dow Corning 478 Fluid (a product of Dow Corning Corporation) on the settling and redispersability is shown in Table VII.
TABLE VII______________________________________ After 4 Days Storage Settling Dow Corning 478 FalloutCoating (Parts)* (Inches) Redispersability______________________________________6-1 0 0.5 Not Redispersible6-2 0.63 0.3 Dispersible6-3 1.25 little Easily Dispersed6-4 1.88 little Easily Dispersed6-5 2.5 little Easily Dispersed______________________________________ *Parts/100 parts latex and Cymel 373. All parts are on day basis.
The data in Table VII show that silica, when used in the coating, has a tendency to settle down due to its higher specific gravity relative to that of the other components. Furthermore, once settled, silica tends to form a cake and is not easily redispersible. The addition of small amounts of Dow Corning 478 to the coating decreases the rate of settling of silica and also makes the amount settled easily dispersible. A uniform dispersion of silica in the coating is necessary to maintain product uniformity and quality.
It is well known in the art that to obtain a good quality, pin-hole free, uniform coating, the coating composition must wet the substrate. Surfactants are often added to waterborne coating compositions to improve their ability to wet a substrate. A number of surfactants were evaluated in the coating compositions of the present invention to impart good wettability across a wide variety of substrates. All substrates contained polyvinyl chloride and varying amounts of plasticizers. The amounts of various surfactants used were the minimum required to achieve good wetting for all three substrates x, y and z. After the application, the coatings were cured at 250� F. for 1 minute in a forced air oven and subjected to 200 scrub cycles with isopropanol. The following results were obtained.
TABLE VIII______________________________________ Isopropanol Scrub Resistance Vinyl SubstrateSample Surfactant Y (Least Z (Most# Surfactant Level* X Plasticizer) Plasticizer)______________________________________7-1 None -- Pass Not Tested Did Not Wet7-2 KM-10-1610.sub.(1) 0.54 Pass Pass Pass7-3 Zonyl FSA.sub.(2) 0.70 Pass Pass Fail7-4 Zonyl FSA.sub.(2) 1.50 Pass Pass Fail7-5 Silwet L77.sub.(3) 7.00 Pass Fail Fail7-6 Silwet 7.00 Pass Fail Fail L7001.sub.(4)7-7 Dowfax 2A1.sub.(5) 4.50 Fail Fail Fail______________________________________ *Parts (dry) per 100 parts (wet) coating .sub.(1) Sodium bis(2ethylhexyl) sulfosuccinate surfactant Permuthane Corporation. .sub.(2) Fluorocarbon Surfactant DuPont .sub.(3) A polyalkyleneoxide modified heptamethyltrisiloxane nonionic surfactant Union Carbide Corporation. .sub.(4) A polyalkyleneoxide modified polydimethysiloxane nonionic surfactant Union Carbide Corporation. .sub.(5) Sodium dodecyl diphenylether disulfonate Dow Chemical Co.
These results shown in Table VIII indicated that "KM-10-1610" was the most effective surfactant (least amount needed to wet all three substrates). Furthermore, it was the only surfactant of the many tried which provides both good wetting and isopropanol scrub resistance for all three substrates.
It was found that the addition of polyvinyl alcohol (PVOH) to the coating composition improves shelf-stability, especially when a more reactive (i.e. partially alkylated) melamine-formaldehyde resin is used. Also, PVOH provides some reduction in gloss. The coatings contained (all parts on dry basis) 90 gms of latex, 10 gms of Cymel 373 melamine-formaldehyde resin (Cytec Corporation), 0.2 gm Drew L198 defoamer, 22.5 gm HP250 silica flatting agent, 1.6 gm KM-10-1610 surfactant, 1.25 gm Dow Corning 478, 6.5 gm p-toluene sulfonic acid and varying amounts of PVOH as listed in Table IX.
TABLE IX______________________________________Example PVOH Gloss Shelf Stability______________________________________8-1 0.0 7.5 <18 hrs8-2 3.2 7.1 <18 hrs8-3 9.8 6.6 26 hrs8-4 12.8 6.0 26 days8-5 15.9 6.1 >6 days8-6 18.1 5.4 >6 days______________________________________
These data clearly show the benefits of PVOH addition for improving shelf-stability and reducing gloss. The addition of PVOH, at the levels tested, had no adverse effect on the isopropanol (IPA) scrub resistance.
The addition of PVOH to the coating was also found to provide increased abrasion resistance to the coating. This is illustrated by the data set forth in Table X.
TABLE X______________________________________ Relative Flatting Gloss Shelf AbrasionExamples Agent PVOH* % Stability Resistance**______________________________________9-1 HP-250 0 5.3 <1 day 49-2 Syloid 820 0 4.7 <1 day 49-3 HP-250 34.0 3.2 >12 days 19-4 Syloid 820 34.0 3.1 >12 days 2______________________________________ *Parts/100 part latex and Cymel 373 (dry basis) **Wyzenbeck Abrasion Test, ASTM D4157 (wire screen), 1000 cycles. Rating on a scale of 1 to 4 (lower the better).
The amount of functional monomers (e.g. hydroxyethyl acrylate (HEA), hydroxypropyl methacrylate (HPMA) in the latex polymer used in the coating must be controlled to provide good shelf-stability to the latex and coating while at the same time obtaining sufficient cure and good coating properties.
A series of latexes were prepared with the monomer ratios set forth in Table XI.
TABLE XI______________________________________ Polystyrene Methylmeth- 2-EthylhexylLatex Seed HEA acrylate Acrylate______________________________________10-1 6 6 62 2610-2 6 8 62 2410-3 6 10 62 2210-4 6 12 60 22______________________________________
Stable latexes were obtained in all cases except 10-4 which coagulated completely in the polymerization bottle. Also Latex 10-3, though stable was significantly more viscous (Brookfield viscosity=1600 cps) than Latex 10-1 (75.5 cps) and 10-2 (267.5 cps). When these latexes were compounded into coatings with Cymel 303 and p-toluene sulfonic acid, the coating from Latex 10-3 was much thicker (paste-like) than the corresponding coatings from the other two latexes. Thick coatings are difficult to process in a production environment.
In separate experiment it was determined that the amount of functional monomer can be as low as 2 pphm (parts per hundred parts monomers) to provide adequate IPA resistance.
TABLE XII______________________________________Polystyrene Methacrylic Methyl 2-EthylhexylLatexSeed HEA Acid methacrylate Acrylate______________________________________11-1 6.0 2.0 0.7 36.7 54.611-2 6.0 4.0 0.7 40.0 49.3______________________________________
Coatings made from Latexes 11-1 and 11-2 (Table XII) were applied to vinyl laminates and cured at 50� F. for 1 minute. Both coatings passed 50 scrubs with IPA.
It was discovered that the addition of chain transfer agents, which lower the molecular weight of the polymer, is detrimental to the performance of the coatings of this invention. This is illustrated in Table XIII which shows that even small amounts of chain transfer agent result in inadequate solvent resistance (isopropanol scrub resistance). The latex monomer composition was 6 pphm polystyrene seed, 62 pphm methylmethacrylate 26 pphm 2-ethylhexyl acrylate and 6 pphm hydroxyethyl acrylate
TABLE XIII______________________________________ IPA Scrub ResistanceExample Sulfole 120* of Coating**______________________________________12-1 0 Pass12-2 0.2 Fail12-3 0.4 Fail______________________________________ *Sodium dodecyl mercaptan chain transfer agent. Parts are in pphm. **The coatings contained (all parts on dry basis) 90 parts latex, 10 part Cymel 303 and 2 parts paratoluene sulfonic acid.
As is apparent from the foregoing, we have discovered water based compositions which are particularly suitable for application as stain resistant/cleanable coatings. These low VOC coatings significantly reduce the use and emission of solvents in the manufacturing environment. The ease of stain removal without the use of harsh solvents is an additional benefit in consumer safety compared to presently used coatings which require more aggressive solvents to remove severe stains.
While in accordance with the patent statutes the best mode and preferred embodiment has been set forth, the scope of the invention is not limited thereto, but rather by the scope of the attached claims.
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|U.S. Classification
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|International Classification
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|Mar 5, 1999
Owner name: GENCORP SERVICES, INC., OHIO
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Many brands offer some type of lip-plumping product, whether it is a balm, gloss, or something simply named "Lip Plumper", but do these types of products really work? Here's what you need to know about lip plumpers so you can protect your precious pout!
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subset: commoncrawl


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Charleston, W.Va. (AP) -- Two adults are in jail after being charged with duct-taping a 2-year-old boy they were supposed to be baby-sitting.
James Usher and Della Jackson both face charges of felony child abuse.
Both were arraigned in Kanawha County magistrate court on Monday.
They're being held at South Central Regional Jail on $100,000 cash bonds.
It could not be immediately determined if either has a lawyer.
Police say they duct-taped the arms, ankle, torso and mouth of a boy they were watching at his mother's Charleston home and took pictures of him.
His mother, Jessica McClure, was not home at the time.
She was subsequently charged with felony child neglect.
McClure is being held at South Central Regional Jail.
(Copyright 2010 by the Associated Press. All rights reserved.)


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Hotels in Mount Baigura
Meet 4 travelers, 1 tour guides and discover 192 photos
Travelers are voting Comfort Hotel Toulouse Sud, Hotel Residence Monne-decroix and InToulouse as the best of 488 hotels in Mount Baigura. There are 120 hotels in Perpignan a city just 227 km from Mount Baigura and 132 hotels in Montpellier which is 259 km distant. The most popular of these are Travel enthusiast MONTPELLIER in Perpignan and French mom in Montpellier. You can find 343 hotels in Midi-Pyrenees and 7832 hotels in the country of France. Our members favorite in Midi-Pyrenees is Travel enthusiast MONTPELLIER and athletic family is the top pick in France. Want more? Check out our map of hotels in Mount Baigura.
Comfort Hotel Toulouse SudTourist Essentials Hotels5 Ave Des Cretes,Ramonville Saint Agne, Toulouse, Midi-Pyrenees 31520, France
Location. Comfort Hotel Toulouse Sud is located in central Ramonville Saint Agne, close to University of Toulouse III. Additional area points of…1
Hotel Residence Monne-decroixTourist Essentials Hotels137 Route De Tarbes, Tournefeuille, 31170, France
Location. Hôtel Résidence Les Pins Galants Toulouse Tournefeuille is a business friendly hotel located in Tournefeuille and local attractions includ…1
InToulouseTourist Essentials Guesthouse1, impasse du professeur Nougayrol 31100 Toulouse, Toulouse, 31100, France
Weclome to InToulouse guesthouse, a great family home in a quiet in a cul de sac,0
Ibis Toulouse UniversiteTourist Essentials HotelsRue Jacques Babinet, Toulouse, 31100, France
Location. Ibis Toulouse Université is located in Toulouse, close to University of Toulouse II, Musee des Augustins, and Place de Capitole. Nearby…1
Campanile Toulouse LabegeTourist Essentials HotelsRue De La Decouverte, Voie N2 B P 132, Labege, 31676, France
Location. Campanile Toulouse Labege is located in Labege, close to University of Toulouse III and Cite de l'Espace. Additional area points of…1
Campanile Toulouse LabegeTourist Essentials HotelsRue De La Decouverte, Labege Innopole Cedex, 31676, France
Hotels are usually nationally recognized brands and rooms will include private baths, telephones, t.v. and basic comfortable furnishings. Rooms typica…1
Appart City Toulouse Diagora LTourist Essentials HotelsRue Jean Rostand, Labege, 31681, France
Residential accommodations that provide a furnished apartment for an employee or guest needing temporary housing on a month-by-month extended lease…1
Park Suites TournefeuilleTourist Essentials Hotels16 Rue Paul Valery, Tournefeuille, 31170, France
Location. Located in Tournefeuille, Park & Suites Confort Toulouse Tournefeuille is in the suburbs with local attractions including…1
Premiere Classe PamiersTourist Essentials HotelsLieu dit la Bouriette, Pamiers, 9100, France
Location. Premiere Classe Pamiers is located in Pamiers and attractions in the region include Chateau de Foix. Hotel Features. Premiere Classe…1
Nature loversTourist Essentials HomestayLAGARDE, 31290, France
We are pleased to welcome you on the road that connects the Mediterranean to the Atlantic Ocean. Nestled in the hills below the village of…81


text:
Atlanta police say the ambulance was found just before midnight Wednesday with its engine still running.
Police say paramedics had left the engine running while they made their call in southeast Atlanta.
Atlanta police Lt. Antonio Clay says nothing was missing from the ambulance when it was found.
Police are hoping that a recording device in the ambulance captured a picture of the thief.


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ive set as static home page of my site the page registration with the shortcode of wp-members plugin inside.
in the sidebar i've placed the widget to log in.
if i type a wrong pass in the filed and then i click on LOGIN, the home page will be reloaded with index.php and i can see ALL MY PRIVATE BLOG...
what's the problem???
i've have installed these plugin:
Hide Update Reminder
Manage Your Posts Only
Hide Update Reminder
WP Custom Search


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[Watch] Here's What Happens When Your Side Chick Crashes Your Wedding
It's a scene out of a Tyler Perry movie.
(Photo: Walden Media)
One of the most important films about challenging our failing education system is back. Won't Back Down, which stars Viola Davis, Maggie Gyllenhaal and Rosie Perez, arrives on DVD today and the cover includes a quote from BET.com.
The film proves that parents and educators can always be revolutionary in their combined efforts. Following two women, a teacher and a student, they erect a charter school to replace their deteriorating local public school.
In the clip below, Viola discusses Won't Back Down and much more.
It's a scene out of a Tyler Perry movie.
A few fellow students have taken to Instagram displaying an appalling lack of remorse


text:
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Baked lemon salmon tucked into fettucine noodles with garlic-sauteed baby spinach and a light, creamy sauce with hints of lemon and Parmesan. … [Read more...]
Salmon with Easy Homemade Honey Barbecue Sauce
Baked salmon smothered in the most delicious homemade honey barbecue sauce that takes all of ten minutes to make. It's sweet and tangy and makes salmon taste pretty close to heavenly. … [Read more...]
Chinese Sesame Salmon
Baked salmon smothered in a sticky Chinese sesame sauce, the very same sauce that's on sesame chicken. The sweet and savory sauce works just as well, if not better, with salmon. The sauce is made stove top and doesn't go on until after the salmon is baked. It's made by … [Read more...]
"Lime in the Coconut" Salmon
Salmon marinated in coconut milk and lime juice is crusted with spicy, lime-infused coconut flakes and toasted cashew crumbs then baked until hot and flaky. It's light and flavorful, easy to make, healthy and delicious. … [Read more...]
Salmon en Croûte with Lemon Dill Sauce
This is a classic French dish with salmon tucked inside puff pastry and baked. En croute is French for 'in crust'. This version includes asparagus that sits right on top of the salmon and gets wrapped up inside the pastry so when you slice it you can see all the layers … [Read more...]


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Both presidential candidates are in the Sunshine State today.
John McCain is speaking to the National Urban League in Orlando today
Barack Obama was speaking at a town hall meeting this morning in St. Petersburg when three men interrupted Obama and began heckling him.
McCain will appear with country music star John Rich at a concert and rally in Panama City this evening and...Obama will hold a town hall meeting in Titusville Saturday
before addressing the National Urban League in Orlando.


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Will Jamie Dimon Keep His Dual Titles?
A second major proxy adviser urged J.P. Morgan Chaseeholders to separate the chairman and chief executive roles and vote out directors who serve on the bank's risk committee.
The recommendations by Glass Lewis follow similar guidance for shareholders from Institutional Shareholder Services and raise the pressure on Chairman and CEO James Dimon ahead of the bank's annual meeting May 21.
Dan Fitzpatrick swings by MoneyBeat with Paul Vigna to discuss the proxy battle to split Jamie Dimon's posts.


text:
- Report: #957588
Report - Rebuttal - Arbitrate
Complaint Review: westchester county cps coretta akrong
westchester county cps coretta akrong85 court street white plains, New York United States of America
westchester county cps coretta akrong good counsel thye unreasonably took my child at birth right out of the delivery room white plains, New York
*General Comment: stay Strong. Everything Will Work Out.
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This report was posted on Ripoff Report on 10/20/2012 09:56 AM and is a permanent record located here: http://www.ripoffreport.com/r/westchester-county-cps-coretta-akrong/white-plains-New-York-10601/westchester-county-cps-coretta-akrong-good-counsel-thye-unreasonably-took-my-child-at-birt-957588. The posting time indicated is Arizona local time. Arizona does not observe daylight savings so the post time may be Mountain or Pacific depending on the time of year.
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#1 General Comment
stay Strong. Everything Will Work Out.
AUTHOR: HGIT - (United States of America)
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Crock Pot - Sour Cream Swiss Steak
Total Time
Prep 10 mins
Cook 5 hrs
DELICIOUS and EASY!! Makes GOOD gravy which is wonderful served over mashed potatoes. Your dinner cooks while you shop or work. Easy preparation!
Ingredients Nutrition
- 680.38 g cube steaks
- 59.14 ml self rising flour
- 44.37 ml vegetable oil
- 1 medium onion, chopped
- 396.89 g can tomatoes, petit diced
- 14.79 ml ketchup
- 14.79 ml Worcestershire sauce
- 1.23 ml garlic powder
- 1.23 ml salt
- 1.23 ml pepper
- 118.29 ml sour cream
- Dredge steak pieces in flour. In a large skillet, brown steak pieces in vegetable oil. Remove and place in bottom of crock pot.
- In a medium size bowl mix all remaining ingredients EXCEPT sour cream. (Do not drain tomatoes.) Pour mixture over steak in pot.
- Turn crock pot on high for 1st hour. Turn to low for remaining 3 to 4 hours.
- Mix in sour cream during last 30 minutes of crock pot cooking time.
- Note: If thicker gravy is desired: In a small bowl mix together 1 tablespoon cornstarch with 2 tablespoons of cold water and mix into pot jucies 5 minutes before serving.
- Wonderful served over mashed potatoes!
- Enjoy!
Most Helpful
I reviewed this a few minutes ago but forgot to do the stars. Definitely 5 star.
This was very easy to prepare and I definitely like the ease of using my crock pot. Meat turned out tender and it was quite similar to my favorite Swiss Stack recipe. I did find the Worcestershire sauce a little too obvious, might just leave it out the next time.
Quick easy and tastey.Enjoyed by the whole family.Thanks for posting.


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Legendary Rap Pioneers The Furious 5 Live in Concert
* Additional fees apply. No coupon or promo codes necessary to enjoy the displayed discount price.
The last date listed for The Furious 5 was Saturday July 6, 2013 / 9:00pm (Doors at 7:00pm).
Currently at B.B. King Blues Club
Strictly Sinatra: A Tribute to Frank Starring Michael Dutra
- Full Price:
- $22.00 - $45.00
- Our Price:
Close your eyes and listen, and you might just think you're back in a supper club in the 1950s. The… More
Venue Details
Reviews & Ratings
Featured review from Brian F.
view more less of this review
If you grew up on the iconic sounds of this group as I did you enjoyed that they can still throw it down like it was 35 years ago. Beat Street Breakdown was a favorite of mine and Melly Mel can still spit it out with fire!
star this review starred report as inappropriate
The event's performance was awesome. The Furious Five certainly came out to give a great show at B.B. Kings and we enjoyed them immensely. Unfortunately the waitress/hostess provided terrible customer service giving more attitude rather than...continued
star this review starred report as inappropriate
The Show was extremely quick-I've never attended a concert that last less than 1 hour, after the last song, everyone thought they weren't finished until the DJ started packing his equipment, that was a little strange-and the cut ALLLLLLLLL the...continued
Quotes & Highlights
Watch the video for "The Message."


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When we have eight or more students in a class who have various levels of learning difficulties or special needs and there is only one education assistant to help, we are being asked in effect to either perform a miracle, or to play God and decide who gets the help and who does not. We cannot do this. We cannot perform those miracles.
If you pay attention to all the ruckus about massages, you may miss the fact that teachers are being asked to give up their Charter rights in exchange for a promise of better learning conditions for students. No amount of massaging a political message can detract from that fact.
Today I'm writing to you about what you've said in response to the breakdown in talks to end the teachers' strike. You said that you want a negotiated deal that taxpayers can afford. This has left me with a lot of questions.
B.C. Education Minister Peter Fassbender has asked the teachers to stop striking now, please. I hate to disappoint you, Mr. Fassbender, but it doesn't matter how nicely you ask. What matters is that you fund public education. Properly.
As a therapist, I specialize in assisting families through separation and divorce, and this entire impasse has reminded me of the dynamics that exist between high conflict parents when they are separating. In the case of a high conflict divorce, the collateral damage is always the children.
My son is in Grade 12 and my daughter is in Grade 2. With the current obscure fate of negotiations, I am anxious not only about my son's future but also about that of all other Grade 12 students in B.C. whose achievements are greatly indebted to the amazing work of their teachers.
What if we looked at the whole concept of benefits in a different way. Who actually benefits when we support students whose brains work differently? We are going to need out-of-the-box kinds of thinking that students with special needs do naturally, all the time. We need special solutions to the special challenges we all face.
The industry needs productive, safe, and enabling parameters to work within, and British Columbians deserve to rest assured that our business leaders and elected representatives are engineering those limits properly -- with a foundation much stronger than that of the Mount Polley tailings pond.
Nearly half of Imperial Metal's donations were made after Christy Clark was sworn in as premier, while $45,720 of Mount Polley's donations came via six separate cheques issued in one week alone in March 2013. Guess bank charges weren't an issue for the company.
Income disparity also means that working and living in the same place is a luxury few of us can afford -- not just in third world countries, but in small Canadian rural communities as well. Ironically, our stronger economy is also leading to a weaker society. We can't be there for one another as much as we once were. We're too busy making money.
Frankly, I don't care if the president would drink a glass of that water. I care if he would let his family drink that water. Wash in it. Use it to water livestock, or his garden. His statements did nothing but give fodder for a new meme: Almost Drinkable.
I'm not a politician but you may want to re-think your strategy with the teachers. Something happened when you locked them out of their classrooms in June. There was lots more conversation -- mostly about you and what your real agenda is when it comes to public education. Teachers shared information and experiences and built up relationships that had not existed before.
That's politics. The public gets irate over the small amounts because they can relate to them. But the funny thing is that politicians who get the small things right generally don't screw up the bigger ones.
That's what makes Ford Nation so extraordinary -- the incredible dichotomy that exists when it comes to criticism of most politicians and criticism of Rob Ford. Ford effectively gets what amounts to a jaw-dropping free pass from his base (in Toronto or in B.C.) nine times out of 10.
The intertwining of lobbyists with a political party's fundraising apparatus is worrisome, because ultimately both sides risk developing a dependency on keeping the other happy and the money flowing. It rarely ends well.
Whatever the final government deal is with the B.C. Teachers Federation (BCTF), and whenever it's settled, the BCTF must quit opposing economic growth if it ever hopes to accomplish its long-term salary and class size goals.


text:
- Report: #1035586
Report - Rebuttal - Arbitrate
Complaint Review: Life-business
Life-businessInternet United States of America
Life-business These people do nothing but harrass you for more money, come to our meetings come see who will be available again, Internet
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I am so glad that the bank that i have didn't let anything go out since they were trying to get me to pay another 60.00 after the first 60.00 they told me that i would get services for free for 3 whole months and that wasn't so, the bank contacted me to let me know that someone was trying to get money.
I am still getting phone calls from one of their people Micca he calls me even after i told him that neither me or my daughter were interested any longer please do not call us, He will call again.
This report was posted on Ripoff Report on 03/17/2013 07:51 PM and is a permanent record located here: http://www.ripoffreport.com/r/Life-business/internet/Life-business-These-people-do-nothing-but-harrass-you-for-more-money-come-to-our-meeting-1035586. The posting time indicated is Arizona local time. Arizona does not observe daylight savings so the post time may be Mountain or Pacific depending on the time of year.
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text:
381 Wharparilla Rd Echuca Vic 3564
Contact AgentNeed a home loan? Just crunching the numbers for you...
- 3
- 1
- 4
Kathy Walker
- 0409 801 740
- 0409 801 740
- View profile
381 Wharparilla Rd Echuca
Country Living
* 3 Bedroom home on 1.6 Hectares (approx 4 acres)
* Updated Kitchen plus separate Meals room
* Spacious Open plan Living Room with polished timber floorboards, wood heater & R/C Air Conditioning
* Open Pergola with paved BBQ area
* 6m x 9m Shed with power & attached 3 car carport plus extra shedding
* Frontage to Bitumen Road and school bus pick up
* Variety of Fruit Trees & established garden with 4 x Rain Water Storage Tanks plus 5.4 Meg Water Right
Property No. 115034403
Page Visits: 2,519
- General Features
- Property Type:House
- Bedrooms:3
- Bathrooms:1
- Indoor Features
- Toilets:2
- Air Conditioning
- Outdoor Features
- Carport Spaces:3
- Garage Spaces:1
- Other Features
- Garden, Polished Timber Floor
Floorplans & Interactive Tours
Details not provided
Thinking of living in echuca?
Explore the prices, people and lifestyle that's on offer.
Are you considering investing in echuca?
Explore growth, yield, demand and other historical insights.
The price of a property that falls in the middle of a total number of s sold over a period of time, based on listings over the preceding 12 months.
Data supplied by RP Data Pty Ltd trading as CoreLogic
This information has been obtained by RP Data Pty Ltd trading as CoreLogic and is subject to the following copyright:
RP Data Pty Ltd trading as CoreLogic Notice/Disclaimer
© 2016 Copyright RP Data Pty Ltd trading as CoreLogic (CoreLogic), Local, State, and Commonwealth Governments. All rights reserved. No reproduction, publication, adaption, modification, public communication, distribution or transmission of the copyrighted materials in this publication is permitted whether in whole or in part. The copyrighted materials in this publication are provided for personal or internal business purposes only unless otherwise agreed in writing.
The information provided in this publication is current as at the publication date only. CoreLogic does not warrant accuracy or completeness in the information it supplies and to the full extent allowed by law excludes any liability for any loss or damage arising from or in connection with the supply or use of the whole or any part of the information in this publication through any cause whatsoever and limits any liability it may have to the amount paid to CoreLogic for the supply of such information.


text:
- Store Home
Small Dogs
For Small Dogs ( Up to 20 lbs. )
Medium Dogs
For Medium Dogs ( 15 - 100 lbs. )
Large Dogs
For Large Dogs ( 25 - 150 lbs. )
- Cats
- Company
- Contact Us
Show off your favorite pattern or match your furry friend. Perfect for your car and house keys, or use them to easily pick out your luggage at the airport. Choose from either a standard split ring style key fob or buckle style - perfect for leaving the car running while skipping into the post office or opening the gate or even for keeping those keys together in your purse!
3/4" wide
Showing reviews 1-5 of 10 | Next
Posted by Unknown on Aug 28th 2016
I wanted a simple Keychain for my new car, and love that it matches my dog! They are built well, and look great!
Posted by Mary Troxell on Dec 14th 2015
Wonderful product very versatile and colorful
Posted by Sheila on Mar 18th 2015
I like the medium size key chain as it you can unclip the two parts. I also like it because it is long and easy to grab, plus its size makes it harder to lose. However, if you phyically have to insert your key into the ignition, the keys might dangle on your leg and bother you. I have a push-button start, so this isn't a problem for me.
Posted by Reta B on Sep 10th 2013
I picked one of your bright colors so I could easily find my keys. And as usual with Lupine products this key chain did not disappoint. We love Lupine.
Posted by Ashley on Jul 16th 2013
This is exactly what I've been looking for. The keychain is durable and the patterns are unique and eye-catching.
Showing reviews 1-5 of 10 | Next


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Ningaloo Whaleshark Swim
Experience wonder up very close and personal with the biggest shark in the world.
Join the Gold Medal-winning whale shark exmouth cruise voted the Best Adventure Tour in Western Australia for a wonder-filled day cruising and diving the Ningaloo Reef - a World Heritage-listed Ningaloo Reef.
Our aim is simple – to delight, educate, entertain and keep each and every one of our guests, and keep them (very) safe and wanting to come back for more. We invite you to join us for an adventure of a lifetime!
A breathtaking experience
Finding you a whale shark is what we are experts at, but there is so much more out there we want to share with you! Migrating whales, manta rays, dolphins, dugongs, turtles, spectacular corals, all shapes and sizes of fish… and so much more.
Come join us for what we aim to make one of the best tours you have ever been on!
More for you
Our own spotter plane normally means your own whaleshark to swim with, not waiting in a line of whaleshark tour boats for a turn.
2 free snorkels on the Ningaloo Reef. PLUS free swimming with the manta rays! Free snorkel gear hire whilst in town too!
Only company offering SCUBA diving OR Try SCUBA divingduring your tour. Or a snorkel scooter safari or mermaid swimming!
Free photos of your whaleshark experience. Hire an underwater camera or buy professional photos from our onboard photographer.
Industry-best Whaleshark Swim Guarantees - come out again for free repeatedly or 3 year sell-able voucher, or ~$140 cash refund.
Our hi-tech masks make snorkelling easy for all. Breath normally with no snorkel in your mouth or water in your snorkel. See more too!


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Take a sneak peek at the new NIST.gov and let us know what you think!
(Please note: some content may not be complete on the beta site.).
NIST Authors in Bold
|Elaine B. Barker;
|Recommendation for Digital Signature Timeliness
|September 23, 2009
|Establishing the time when a digital signature was generated is often a critical consideration. A signed message that includes the (purported) signing time provides no assurance that the private key was used to sign the message at that time unless the accuracy of the time can be trusted. With the appropriate use of digital signature-based timestamps from a Trusted Timestamp Authority (TTA) and/or verifier-supplied data that is included in the signed message, the signatory can provide some level of assurance about the time that the message was signed.
|Special Publication (NIST SP) - 800-102
|30 pp.
|digital signatures, timeliness, timestamp, Trusted Timestamp Authority
|Research Areas:
|Information Technology, Cybersecurity
|PDF version:
|Click here to retrieve PDF version of paper (261KB)


text:
- Report: #430474
Report - Rebuttal - Arbitrate
Complaint Review: Lime Wire
Lime Wirelimewire.com Nationwide U.S.A.
Lime Wire Lime Wire unusable and unreachable Internet
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Elmira, New York
This report was posted on Ripoff Report on 03/03/2009 05:38 PM and is a permanent record located here: http://www.ripoffreport.com/r/Lime-Wire/nationwide/Lime-Wire-Lime-Wire-unusable-and-unreachable-Internet-430474. The posting time indicated is Arizona local time. Arizona does not observe daylight savings so the post time may be Mountain or Pacific depending on the time of year.
Ripoff Report has an exclusive license to this report. It may not be copied without the written permission of Ripoff Report.
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- Only search one name at a time if Company has many AKA's.
Advertisers above have met our
strict standards for business conduct.


text:
Definition of luteous in English:
Of an orange-yellow or greenish yellow colour.
Example sentences
- The stromatal surface color is luteous while developing but becomes dull black when fully mature, with only traces of luteous remnants found in places.
- Just before hatching, the spots disappear, the ground colour becomes pale lemon yellow, and the shell is luteous.
For editors and proofreaders
Line breaks: lu|teous
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Comments that don't adhere to our Community Guidelines may be moderated or removed.
= trending


text:
George Miller
Published: Friday, September 10, 2010 at 9:37 a.m.
Last Modified: Friday, September 10, 2010 at 9:37 a.m.
George D. "Hoss" Miller, 75, a native of Iota and a resident of Gray, died peacefully with his loving family and friends from lung cancer.
Visitation will be from 6 to 10 p.m. today at Falgout Funeral Home Chapel in Houma and from 8 a.m. to funeral time Saturday at St. Bridget Catholic Church. Mass will be held at 11 a.m. Saturday at the church, with burial in Garden of Memories Cemetery.
He is survived by his wife of 51 years, Katherine L. Miller; two sons, Jeff and wife, Francine, and Chris and wife, Chantel; four daughters, Annette Soileau and husband, Randy, Roxanne and husband, Pat Soileau, Brenda Berteau and Betty Hebert; one brother, Fred Miller; three sisters, Bunny Touchet, Nell Pellegrin and Chick Miller; 19 grandchildren; and 10 great-grandchildren.
He was preceded in death by his parents, Jeff and Louise Reed Miller; two brothers, Bob and Rodney Miller; and one sister, Jean Hebert.
He was a U.S. Air Force veteran. He was an avid LSU fan and loved life and family to the fullest.
Thanks to our Angels ACC Clinic and Leonard Chabert.
Falgout Funeral Home is in charge of arrangements.
Reader comments posted to this article may be published in our print edition. All rights reserved. This copyrighted material may not be re-published without permission. Links are encouraged.


text:
I am running WordPress 3.0 Multisite. Everything is perfect on the main site, but the other sites cannot upload media. Actually, they can UPLOAD it, but it won't display. This is what happens after it is uploaded:
I need a fix for this ASAP, as I have a line of bloggers ready to join my network.
Thanks for any help you can provide,


text:
Let our team be your Business IT Helpdesk.
MinnDak Computer Services LLC © All Rights Reserved.
Technology Planning
We learn about your business and help design a plan for your growth.
Disaster Recovery
We plan for failure and craft a response plan specific to your business.
Change Control
Controlling Changes through our proven process reduces the risk of failure.


text:
JFK Website (3)
Digital Archives (0)
Sortable End Date: 20041203
Boston, MA- The Museum at the John F. Kennedy Presidential Library will honor our nation's war heroes this Veterans Day by giving all United States Veterans free admission to the Museum. Veterans will be given free admission from Veterans Day through Sunday November 13th.
Boston, MA- The John F. Kennedy Library Foundation announced today that the 2006 John F. Kennedy Profile in Courage Essay Contest is now open and accepting submissions from U.S. high school students enrolled in grades nine through twelve. The deadline for entries is Saturday, January 7, 2006.
The John F. Kennedy Library Foundation will welcome back former employee Shelley Sommer, author of John F. Kennedy: His Life and Legacy, a new book written specifically for middle school aged children on the life of President John F. Kennedy, at a book reading for 150 school children at the John F. Kennedy Presidential Library and Museum on Mond...
Search powered by Oracle Endeca ®.
JOHN F. KENNEDY PRESIDENTIAL LIBRARY AND MUSEUMColumbia Point, Boston MA 02125 (617) 514-1600


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The bold and the beautiful Rick Owens Geobasket sneakers are the exaggerated high top you either love or hate. And if you're a part of the former, you absolutely adore the pony hair version that dropped this summer. Motherfuckers really can't tell you nothing if you can pull off these risky kicks.
The 20 Best Designer Sneakers of 2013
Rick Owens Geobasket Pony Hair
Watch Now


text:
You are a fan of artistic ikuto ? Come to discover the best forums artistic ikuto on the internet and share your experience with a community fan of artistic ikuto . You can also build a forum artistic ikuto and create your online discussion.
A drama free place to make friends, exchange tags, and just have fun. Come in and make yourself at home.
#artistic, passions, drama, free, place, friends, exchange, tags


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Watermelon Spritzy
- 2 cups watermelon, chopped or watermelon puree
- 2 cups lemon-lime soda, cold
- 1 tablespoon grenadine
- 1/2 cup frozen mixed berries, optional, use instead of ice
- Fresh mint sprigs, for garnish
Put watermelon, lemon-lime soda, and grenadine into a blender.
Blend for 20 to 30 seconds. Use a strainer to strain into pitcher.
Divide frozen berries between 4 glasses. Pour juice over berries. Garnish with a straw and a sprig of mint.
Recipe courtesy of Sandra Lee, 2007


text:
Skip to content
© iStockPhoto/vm
At EDINA we run a programme of training courses, both on-site and online webinars. We also attend conferences and on occasion run them.
See also a list of presentations, publications and videos from our staff.
All enquires about EDINA training courses and events should be directed to firstname.lastname@example.com
No events are scheduled at the present time.
EDINA Geoforum
7 September, University of Edinburgh
10:00 to 16:15, Institute of Geography, Drummond Street, Edinburgh
Programme TBA
GeoForum is a free event aimed at lecturers, researchers and support staff who promote and support the use of maps and geo-data at their institution.


text:
I just installed WordPress, BudyPress and rtMedia. I create a page and added the image upload shortcode as follows: [rtmedia_uploader] I do see the upload box, but it is missing the 'Upload' button. Even after selecting some images, there is no Upload button - see screenshot:
I have tried to adjust the shortcode by parsing a context, etc, but that didn't help. FYI, am using the default WP TwentyTwelve theme.
Any suggestions?