text:
Protective epoxy overcoat for imaging elements
The present invention relates to imaged elements having a protective overcoat that resists fingerprints, common stains, and spills. In particular, an overcoat composition comprising water-dispersible epoxy-functional particles is coated over an imaging element, including photographic elements and recording media. In one embodiment, a photographic element includes a support, at least one silver halide emulsion layer superposed on the support and a processing-solution-permeable protective overcoat overlying the silver halide emulsion layer that, after fusing, becomes water-resistant in the final product. The present invention is also directed to a method of making a print involving developing the photographic element and subsequently fusing the overcoat.
Latest Eastman Kodak Company Patents:
The present invention relates to imaged elements having a protective overcoat that resists fingerprints, common stains, and spills. In particular, the invention is directed to an overcoat composition comprising a water-dispersible epoxy-functional latex is coated over an imaged element, including photographic elements and recording media. A method of forming a protective overcoat on an imaging element is also disclosed.BACKGROUND OF THE INVENTION
Gelatin has been used extensively in a variety of imaging elements as the binder because of its many unique and advantageous properties. For example, its property of water swellability allows processing chemistry to be carried out to form silver halide-based photographic images, and its hydrophilic nature allows gelatin to function as an ink-receiver in ink-jet recording media. For a photographic element, an aqueous solution needs to penetrate the surface of the element to contact the silver halide and couplers necessary for dye image formation. For an ink-jet recording element, an aqueous dye solution needs to be absorbed very quickly by the element or media to fix the dye image. Therefore, water-soluble polymers or materials that have affinity with water are proven to be the binders of choice for these imaging elements. However, while these materials are good for image development, they are not strong enough to resist mechanical damage such as scratching, tearing, and other types of deformation. Furthermore, the imaged elements, after image formation is complete, have very little resistance to fingerprints or to stains from food and drink spills. Imaging elements with exposed gelatin-containing materials, no matter if they are formed on transparent or reflective media, need to be handled with extreme care so as not to come into contact with aqueous solutions that may damage the images. Accidental spillage of common household solutions such as coffee, punch, or even plain water can damage imaged elements such as ink-jet, electrophotographic, or photographic prints.
There have been attempts over the years to provide protective layers for gelatin based photographic systems that will protect the images from damage by water or aqueous solutions. U.S. Pat. No. 2,173,480 describes a method of applying a colloidal suspension to moist film as the last step of photographic processing before drying. A series of patents describes methods of solvent coating a protective layer on the image after photographic processing is completed and are described in U.S. Pat. Nos. 2,259,009, 2,331,746, 2,798,004, 3,113,867, 3,190,197, 3,415,670 and 3,733,293. U.S. Pat. No. 5,376,434 describes a protective layer formed on a photographic print by coating and drying a latex on a gelatin-containing layer bearing an image. The latex is a resin having a glass transition temperature of from 30° C. to 70° C. The application of UV-polymerizable monomers and oligomers on processed image followed by radiation exposure to form crosslinked protective layer is described in U.S. Pat. No. 4,092,173. A drawback for both the solvent coating method and for the radiation cure method is the health and environmental concern of those chemicals or radiation to the coating operator. Another drawback is that the photographic materials need to be coated after the processing step. Thus, the processing equipment needs to be modified and the personnel running the processing operation need to be trained to apply the protective coating.
Alternatively lamination can be used to provide an imaged element with resistance to scratch, water, and stain resistance. Lamination involves placing a durable and/or adhesive protective layer coated on a suitable support to the image which is to be protected. The support of the protective coating may remain permanently adhered or it may subsequently be peeled off leaving only the protective layer adhered to the image. Lamination has several disadvantages in that it brings about an added expense associated with coating an additional support. In addition, air pockets may be trapped during the laminating step leading to image defects.
Protective coatings that need to be applied to the image after it is formed, several of which were mentioned above, adds a significant cost to the final imaged product. A number of patents have been directed to water-resistant protective coatings that can be applied to a photographic element prior to development. For example, U.S. Pat. No. 2,706,686 describes the formation of a lacquer finish for photographic emulsions, with the aim of providing water- and fingerprint-resistance by coating the light-sensitive layer, prior to exposure, with a porous layer that has a high degree of water permeability to the processing solutions. After processing, the lacquer layer is fused and coalesced into a continuous, impervious coating. The porous layer is achieved by coating a mixture of a lacquer and a solid removable extender (ammonium carbonate), and removing the extender by sublimation or dissolution during processing. The overcoat as described is coated as a suspension in an organic solvent, and thus is not desirable for large-scale application. More recently, U.S. Pat. No. 5,853,926 to Bohan et al. discloses a protective coating for a photographic element, involving the application of an aqueous coating comprising polymer particles and a soft polymer latex binder. This coating allows for appropriate diffusion of photographic processing solutions, and does not require a coating operation after exposure and processing.
U.S. Pat. No. 5,856,051 describes the use of hydrophobic particles with gelatin as the binder in an overcoat formulation. This invention demonstrated an aqueous coatable, water-resistant protective overcoat that can be incorporated into the photographic product, allows for appropriate diffusion of photographic processing solutions, and does not require a coating operation after exposure and processing. The hydrophobic polymers exemplified in U.S. Pat. No. 5,856,051 include polyethylene have a melting temperature (Tm) of 55 to 200° C., and are therefore capable of forming a water-resistant layer by fusing the layer at a temperature higher than the Tm of the polymer after the sample has been processed to generate the image. The coating solution is aqueous and can be incorporated in the manufacturing coating operation without any equipment modification.
It can be seen that various approaches have been attempted to obtain an imaged imaging element with resistance to water and mechanical damages. However, the aforementioned prior art references are deficient with regarding to simultaneously satisfying the performance, environmental, and cost requirements. Also, in recent years, the use by the public of various printing and imaging technologies in the publishing industry as well as at home increasingly becomes more popular. It becomes increasingly more desirable to provide protection for the imaged or printed documents against abrasion, transfer cover materials, water or alcohol spills, ink smear, or other image print degradation processes and detrimental effects from the surroundings. It would be desirable to obtain a water-resistant imaged element with a protective overcoat with superior properties that avoids the problems and limitations of the prior art.SUMMARY OF THE INVENTION
The present invention relates to a protective overcoat for an imaged element that provides water resistance, fingerprint resistance, and the like. This protective overcoat composition comprises epoxy-containing particles comprising at least 50% by dry weight of a solid epoxy compound or resin and which particles having a glass transition temperature of greater than 20° C. and a mean particle size of less than five microns. The overcoat composition further comprises, in the epoxy-containing particle, a polymer having acid groups. The protective overcoat composition also comprises a binder material for the epoxy-containing particles.
In one embodiment of the invention, the overcoat composition applied to the imaging element comprises 30 to 95 weight percent, based on the dry laydown of the overcoat, of water-dispersible polymer epoxy-containing particles having an average of between 0.01 to 0.5 micrometers, said water-dispersible polymer being characterized by a Tg (glass transition temperature) of greater than 20° C. and 5 to 70 percent of binder. The balance can be up to and the balance materials such as surfactants, lubricants, thickeners. In the case of a photographic element, the imaging element comprises a support, at least one silver-halide emulsion layer superposed on the support, and overlying the silver-halide emulsion layer, a processing-solution-permeable overcoat composition that can be coated onto the imaging element during manufacturing and that does not inhibit photographic processing.
Another aspect of the invention provides for a method of forming an image in the imaging element described above and converting the overcoat into a water-resistant coating, including the use of fusing to convert the overcoat to a water-resistant protective overcoat.DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides a simple and inexpensive way to improve the water, stain and abrasion resistance of imaged elements. In accordance with the invention, a nascently protective overcoat is applied over an imaging element prior to image formation or processing. In particular, an overcoat according to the present invention is present over the emulsion side of photographic products or the image-receiving side of image-recording media, particularly photographic prints or ink-jet prints of real-life images, which prints may encounter frequent handling and abuse by end users.
By the term “water-resistant” is meant herein that, after ordinary processing for image formation, an imaged element does not imbibe water. Water-based stains that can discolor the imaged side of the element is prevented or minimized.
By the term “elevated temperature”, as used in this application, to dry and/or facilitate coalescence of the water-dispersible polymer, is herein meant a temperature of from 30 to 100° C., preferably 45 to 60° C. In contrast, fusing generally requires simultaneous application of heat and pressure, for example employing a pressure roller or belt. Drying of the imaged element before fusing is recommended. Fusing generally requires higher temperatures, typically above the boiling point of water, usually above 100° C.
The present invention provides an improved overcoat for the imaged side of an imaged element or material, including photographic prints, which encounter frequent handling and abuse by end users. The overcoat is made from an overcoat formulation comprising 30 to 95% by weight (based on the dry laydown of the overcoat) of water-dispersible epoxy-containing particles of 0.01 to 0.5 micrometers in average size and 5 to 70% by weight of a hydrophilic polymer (based on the dry laydown of the overcoat).
In one embodiment of the invention, the applied overcoat composition of the photographic element comprises 30 to 95% by weight of solids, preferably 60 to 90 weight percent, of water-dispersible polymer particles having an average particle size of less than 500 nm and a Tg of greater than 20° C., preferably from 20° C. to 70° C., and 5 to 70%, by weight of solids, preferably 10 to 40 weight percent, of a hydrophilic polymer; wherein the weight ratio of the water-dispersible epoxy-containing particles to the hydrophilic polymer is from 20:80 to 95:5, preferably from 40:60 to 90:10, more preferably between 50:50 and 80:20, whereby the overcoat forms a water-resistant overcoat upon fusing, after image formation, namely by heating the image element under pressure to a temperature of at least 100° C. The epoxy particles of the invention have a mean size of less than 5 microns, preferably less than 2 microns.
The epoxy-containing particles comprises a material, a compound or resin, having a 1,2-epoxy functionality, more particularly, having on average greater than about 1.5 epoxide groups per molecule (on a measured basis). The epoxy material can be saturated or unsaturated, linear or branched, aliphatic, cycloaliphatic, aromatic or heterocyclic, and may bear substituents which do not materially interfere with the reaction with the carboxylic acid. Such substituents can include bromine or fluorine. The epoxy material may be monomeric or polymeric. Suitable epoxy resins include glycidyl ethers prepared by reacting epichlorohydrin with a compound containing at least 1.5 aromatic hydroxyl groups carried out under alkaline reaction conditions. Examples of other epoxy resins suitable for use in the invention include diglycidyl ethers of dihydric compounds, epoxy novolacs (substituted or unsubstituted phenyl-containing epoxy materials) and cycloaliphatic epoxies. Generally, epoxy resins contain a distribution of compounds with a varying number of repeat units.
Preferably, the epoxy material is a resin that is a diglycidyl ether of a dihydric phenol, a diglycidyl ether of a hydrogenated dihydric phenol, an aliphatic glycidyl ether, an epoxy novolac, or a cycloaliphatic epoxy. Diglycidyl ethers of dihydric phenols can be produced, for example, by reacting an epihalohydrin with a dihydric phenol in the presence of an alkali. Examples of suitable dihydric phenols include: 2,2-bis(4-hydroxyphenyl) propane(bisphenol-A); 2,2-bis(4-hydroxy-3-tert-butylphenyl) propane; 1,1-bis(4-hydroxyphenyl) ethane; 1,1-bis(4-hydroxyphenyl) isobutane; bis(2-hydroxy-1-naphthyl) methane; 1,5-dihydroxynaphthalene; 1,1-bis(4-hydroxy-3-alkylphenyl)ethane and the like. Suitable dihydric phenols can also be obtained from the reaction of phenol with aldehydes such as formaldehyde (bisphenol-F). Diglycidyl ethers of dihydric phenols include advancement products of the above diglycidyl ethers of dihydric phenols with phenolic compounds such as bisphenol-A, such as those described in U.S. Pat. Nos. 3,477,990 and 4,734,468. Diglycidyl ethers of hydrogenated dihydric phenols can be produced, for example, by hydrogenation of dihydric phenols followed by glycidation reaction with an epihalohydrin in the presence of a Lewis acid catalyst and subsequent formation of the glycidyl ether by reaction with sodium hydroxide.
Aliphatic glycidyl ethers can be produced, for example, by reacting an epihalohydrin with an aliphatic diol in the presence of a Lewis acid catalyst followed by conversion of the halohydrin intermediate to the glycidyl ether by reaction with sodium hydroxide. Examples of suitable aliphatic glycidyl ethers include for example, diglycidyl ethers of 1,4 butanediol, neopentyl glycol, cyclohexane dimethanol, hexanediol, polypropylene glycol, and like diols and glycols; and triglycidyl ethers of trimethylol ethane and trimethylol propane. Epoxy novolacs can be produced by condensation of formaldehyde and a phenol followed by glycidation by reaction of an epihalohydrin in the presence of an alkali. The phenol can be, for example, phenol, cresol, nonylphenol and t-butylphenol. Cycloaliphatic epoxies can be produced by epoxidizing a cycloalkene-containing compound with greater then one olefinic bond with peracetic acid.
Commercial examples of preferred epoxy resins include, for example, EPON™ resin 1001F, 1002F, 1004F, 1007F, 1009F, 2002, 2003, 2004, 2005, 2012, 2014, 2024, 2042, 3001, 3002 available from Shell Chemical Company, and epoxy cresol novolac resin (poly((o-cresyl glycidyl ether)-co-formaldehyde)) available from Sigma-Aldrich Chemical Co.
In one embodiment of the present invention, the water-dispersible epoxy particles, may comprise, in addition to the epoxy material, a substantially amorphous, thermoplastic polymer having carboxylic acid groups, which polymer can be characterized by an acid number. Preferably, the acid number is less than or equal to 250, more preferably less than or equal to 100. Such carboxylated thermoplastic polymers are preferably prepared by conventional free radical polymerization techniques from at least one ethylenically unsaturated monomer and at least one ethylenically unsaturated acid monomer. The choice of the unsaturated monomer(s) is dictated by the intended end use of the coating composition and is practically unlimited. A variety of acid monomers can be used. Their selection is dependent on the desired final polymer properties.
This acid monomer can be an ethylenically unsaturated acid, mono-protic or diprotic, anhydride or monoester of a dibasic acid, which is copolymerizable with the other monomer(s) used to prepare the polymer. The most preferred acid monomers are acrylic acid, methacrylic acid, and itaconic acid.
Preferably, the acid number of the carboxylated thermoplastic polymers is between 30 and 250, preferably between 30 and 200. The acid number is the number of milligrams of potassium hydroxide required to neutralize one gram of the polymer. For purposes of illustration, an acid number of 100 corresponds to the presence in the polymer of either 12.8% acrylic acid, 15.3% of methacrylic acid, 11.5% of itaconic acid, or 10.3% of maleic or fumaric acid.
Ethylenically unsaturated monomers which can be used for preparing a carboxylated thermoplastic polymer include virtually all monomers capable of undergoing addition polymerization to produce polymers free of ionic charge groups and essentially water-insoluble. Typical useful monomers thus include, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, n-octyl acrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, nonyl acrylate, benzyl methacrylate, 2-hydroxypropyl methacrylate acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinylidene chloride, vinyl chloride, styrene, t-butyl styrene, vinyl toluene, butadiene, isoprene, and the like.
The polymerization process is initiated in general with free radical initiators. Free radicals of any sort may be used. Preferred initiators include persulfate, peroxides, azo compounds, and redox initiators. The amount of initiator can vary from 0.01% to 2% by the weight of monomer, but is preferably from 0.03 to 1% by weight thereof. Organic peroxides and organic peresters include, for example, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy)hexine-3, 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butlyperisobutylate, tert-butyl per-secoctoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, and azo compounds include, for example, azobisisobutylnitrile and dimethyl azoisobutylate.
The epoxy-containing particles of the invention can be prepared by various methods known in the art. For example, they can be prepared by pulverizing and classifying the particle material or by spray drying of a solution containing the particle material, including a epoxy resin, followed by redispersing the resultant particles in water using a dispersant. They can be prepared by a suspension technique that consists of dissolving the particle material, including an epoxy compound in, for example, a water immiscible solvent, dispersing the solution as fine liquid droplets in an aqueous solution, and removing the solvent by evaporation or other suitable techniques. They can be prepared by mechanically grinding the particle material, including an epoxy compound, in water to a desired particle size in the presence of a dispersant, heating the epoxy-containing particles dispersed in water to above their melting points, and cooling the melted particles in water to form a stable dispersion. They can be prepared by the so-called “atmospheric emulsification” and “pressure emulsification” techniques. The atmospheric process can be used to prepare epoxy-containing dispersions for epoxy resins with melting points below the boiling point of water. The process typically consists of melting an epoxy compound and a surfactant together. Optionally a base is added to the melt. Hot water is then slowly added to the epoxy melt at vigorous agitation. Pressure emulsification is generally needed for epoxy resins with a melting point greater than 100° C. It is similar to the atmospheric process except at temperature above the water boiling point. Vessels capable of withstanding high pressure are normally needed for such a method.
Various dispersants and surfactants known in the art can be used as stabilizers. The dispersants can be nonionic, anionic, and cationic, and can be polymeric and are used as high as 20% of the epoxy resin. Because such surfactants are potential of causing other problems, the minimum amount of surfactant should be used. Commercial dispersions of epoxy resins often contain a minor amount of surfactant. If the dispersion of epoxy material coagulates or coalesces, then addition of measured amounts of surfactant to freshly prepared dispersions or to the aqueous phase preparatory to formation of the dispersion can be used to assess the stability of the dispersion. Most preferably, the dispersion will be stable with regards to sedimentation of the epoxy-containing dispersed phase. However, in the context of the subject invention, the term “stable” refers to a dispersion where the epoxy resin particles do not coalesce or coagulate, but remain substantially in distinct particles. If such particles sediment upon storage, they may be easily redispersed by shaking or moderate agitation. If, however, the particles coalesce, they cannot be redispersed without high shear mixing for prolonged periods of time.
Commercially available epoxy dispersions may be used in the practice of the invention. Such dispersions are available from a number of manufacturers, for example from Ciba-Geigy as ECN-1400®, a dispersion of epoxy novolac ECN 1299® in water; and Epi-Rez.RTM. 35201®, a dispersion of a solid DGEBA® epoxy resin, CMD W50-3519®, an elastomer modified epoxy dispersion, and W55-50033® or SU-3® epoxy dispersion, all available from Rhone-Poulenc.
A preferred method of making epoxy-containing particles for a coating composition according to one embodiment of the present invention comprises (1) dissolving into a volatile solvent mixture an oil-soluble epoxy-functional compound and a polymer having an acid number greater than 30 and less than 250 and optionally a surfactant, (2) adding to the organic solvent medium in a base to neutralize the acid groups to a degree of neutralization less than 95%, preferably less than 90%, (3) dispersing the resulting organic phase into an aqueous medium optionally containing a surfactant, and (4) removing the volatile solvent mixture. Preferably, the volatile solvent mixture comprises a water immiscible organic solvent as the major component and a water miscible organic solvent as a minor component. Such a process advantageously provides very fine submicron particles having a narrow particle size distribution. The dispersions also have excellent stability during storage.
The protective overcoat preferably comprises, in addition to the water-dispersible epoxy particles described above, at least one hydrophilic polymer as a binder. Examples of hydrophilic polymers that may be added include polyvinyl alcohol, cellulose ethers, poly(N-vinyl amides), polyacrylamides, polyesters, poly(ethylene oxide), dextrans, starch, uncrosslinked or crosslinked gelatin, polyvinylpyrollidone, whey, albumin, poly(acrylic acid), poly(ethyl oxazolines), alginates, gums, poly(methacrylic acid), poly(oxymethylene), poly(ethyleneimine), poly(ethylene glycol methacrylate), poly(hydroxy-ethyl methacrylate), poly(vinyl methyl ether), poly(styrene sulfonic acid), poly(ethylene sulfonic acid), poly(vinyl phosphoric acid) and poly(maleic acid) and the like. Such materials are included in “Handbook of Water-Soluble Gums and Resins” by Robert l. Davidson (McGraw-Hill Book Company, 1980) or “Organic Colloids” by Bruno Jirgensons (Elsvier Publishing Company, 1958). In a preferred embodiment, the polymer is gelatin, which polymer has been found to yield coatings that are relatively uniform and to enhance the diffusion rate of the developer into the underlying emulsions, in the case of photographic elements.
The protective overcoat, after fusing, should be clear, i.e., transparent, and is preferably colorless. But it is specifically contemplated that the polymer overcoat can have some color for the purposes of color correction, or for special effects, so long as it does not detrimentally affect the formation or viewing of the image through the overcoat. Thus, there can be incorporated into the polymer a dye that will impart color or tint. In addition, additives can be incorporated into the polymer that will give the overcoat various desired properties. For example, a UV absorber may be incorporated into the polymer to make the overcoat UV absorptive, thus protecting the image from UV induced fading. Other compounds may be added to the coating composition, depending on the functions of the particular layer, including surfactants, emulsifiers, coating aids, lubricants, matte particles, rheology modifiers, crosslinking agents, antifoggants, inorganic fillers such as conductive and nonconductive metal oxide particles, pigments, magnetic particles, biocide, and the like. The coating composition may also include a small amount of organic solvent, preferably the concentration of organic solvent is less than 1 percent by weight of the total coating composition. The invention does not preclude coating the desired polymeric material from a volatile organic solution or from a melt of the polymer.
Examples of coating aids include surfactants, viscosity modifiers and the like. Surfactants include any surface-active material that will lower the surface tension of the coating preparation sufficiently to prevent edge-withdrawal, repellencies, and other coating defects. These include alkyloxy- or alkylphenoxypolyether or polyglycidol derivatives and their sulfates, such as nonylphenoxypoly(glycidol) available from Olin Matheson Corporation or sodium octylphenoxypoly(ethyleneoxide) sulfate, organic sulfates or sulfonates, such as sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium bis(2-ethylhexyl) sulfosuccinate (Aerosol® OT commercially available from American Cyanamide, Wayne, N.J.), and alkylcarboxylate salts such as sodium decanoate.
The surface characteristics of the overcoat are in large part dependent upon the physical characteristics of the polymers which form the continuous phase and the presence or absence of solid, nonfusible particles. However, the surface characteristics of the overcoat also can be modified by the conditions under which the surface is optionally fused. For example, in contact fusing, the surface characteristics of the fusing element that is used to fuse the polymers to form the continuous overcoat layer can be selected to impart a desired degree of smoothness, texture or pattern to the surface of the element. Thus, a highly smooth fusing element will give a glossy surface to the imaged element, a textured fusing element will give a matte or otherwise textured surface to the element, a patterned fusing element will apply a pattern to the surface of the element, etc.
Matte particles well known in the art may also be used in the coating composition of the invention, such matting agents have been described in Research Disclosure No. 308119, published December 1989, pages 1008 to 1009. When polymer matte particles are employed, the polymer may contain reactive functional groups capable of forming covalent bonds with the binder polymer by intermolecular crosslinking or by reaction with a crosslinking agent in order to promote improved adhesion of the matte particles to the coated layers. Suitable reactive functional groups include hydroxyl, carboxyl, carbodiimide, epoxide, aziridine, vinyl sulfone, sulfinic acid, active methylene, amino, amide, allyl, and the like.
In order to reduce the sliding friction of the photographic elements in accordance with this invention, the overcoat composition may contain fluorinated or siloxane-based components and/or the coating composition may also include lubricants or combinations of lubricants. Typical lubricants include (1) silicone based materials disclosed, for example, in U.S. Pat. Nos. 3,489,567, 3,080,317, 3,042,522, 4,004,927, and 4,047,958, and in British Patent Nos. 955,061 and 1,143,118; (2) higher fatty acids and derivatives, higher alcohols and derivatives, metal salts of higher fatty acids, higher fatty acid esters, higher fatty acid amides, polyhydric alcohol esters of higher fatty acids, etc., disclosed in U.S. Pat. Nos. 2,454,043; 2,732,305; 2,976,148; 3,206,311; 3,933,516; 2,588,765; 3,121,060; 3,502,473; 3,042,222; and 4,427,964, in British Patent Nos. 1,263,722; 1,198,387; 1,430,997; 1,466,304; 1,320,757; 1,320,565; and 1,320,756; and in German Patent Nos. 1,284,295 and 1,284,294; (3) liquid paraffin and paraffin or wax like materials such as carnauba wax, natural and synthetic waxes, petroleum waxes, mineral waxes, silicone-wax copolymers and the like; (4) perfluoro- or fluoro- or fluorochloro-containing materials, which include poly(tetrafluoroethylene), poly(trifluorochloroethylene), poly(vinylidene fluoride, poly(trifluorochloroethylene-co-vinyl chloride), poly(meth)acrylates or poly(meth)acrylamides containing perfluoroalkyl side groups, and the like. Lubricants useful in the present invention are described in further detail in Research Disclosure No.308119, published December 1989, page 1006.
The support material used with this invention can comprise various polymeric films, papers, glass, and the like. The thickness of the support is not critical. Support thicknesses of 2 to 15 mils (0.002 to 0.015 inches) can be used. Biaxially oriented support laminates can be used with the present invention. These supports are disclosed in commonly owned U.S. Pat. Nos. 5,853,965, 5,866,282, 5,874,205, 5,888,643, 5,888,681, 5,888,683, and 5,888,714, incorporated in their entirety by reference herein. These supports include a paper base and a biaxially oriented polyolefin sheet, typically polypropylene, laminated to one or both sides of the paper base. At least one photosensitive silver halide layer is applied to the biaxially oriented polyolefin sheet.
The coating composition of the invention can be applied by any of a number of well known techniques, such as dip coating, rod coating, blade coating, air knife coating, gravure coating and reverse roll coating, extrusion coating, slide coating, curtain coating, and the like. After coating, the layer is generally dried by simple evaporation, which may be accelerated by known techniques such as convection heating. Known coating and drying methods are described in further detail in Research Disclosure No. 308119, Published December 1989, pages 1007 to 1008. Preferably, a commercial embodiment involve simultaneous co-extrusion. The laydown of the overcoat will depend on its field of application. For a photographic element, the laydown of the polyurethane-containing copolymer is suitably at least 0.54 g/m2 (50 mg/ft2), preferably 1.08 to 5.38 g/m2 (100 to 500 mg/ft2), most preferably 1.61 to 3.23 g/m2 (150 to 300 mg/ft2). After applying the coating composition to the support, it may be dried over a suitable period of time, for example 2 to 4 minutes.
Photographic elements can contain conductive layers incorporated into multilayer photographic elements in any of various configurations depending upon the requirements of the specific photographic element. Preferably, the conductive layer is present as a subbing or tie layer underlying a magnetic recording layer on the side of the support opposite the photographic layer(s). However, conductive layers can be overcoated with layers other than a transparent magnetic recording layer (e.g., abrasion-resistant backing layer, curl control layer, pelloid, etc.) in order to minimize the increase in the resistivity of the conductive layer after overcoating. Further, additional conductive layers also can be provided on the same side of the support as the photographic layer(s) or on both sides of the support. An optional conductive subbing layer can be applied either underlying or overlying a gelatin subbing layer containing an antihalation dye or pigment. Alternatively, both antihalation and antistatic functions can be combined in a single layer containing conductive particles, antihalation dye, and a binder. Such a hybrid layer is typically coated on the same side of the support as the sensitized emulsion layer. Additional optional layers can be present as well. An additional conductive layer can be used as an outermost layer of an photographic element, for example, as a protective layer overlying an image-forming layer. When a conductive layer is applied over a sensitized emulsion layer, it is not necessary to apply any intermediate layers such as barrier or adhesion-promoting layers between the conductive overcoat layer and the photographic layer(s), although they can optionally be present. Other addenda, such as polymer latices to improve dimensional stability, hardeners or cross-linking agents, surfactants, matting agents, lubricants, and various other well-known additives can be present in any or all of the above mentioned layers.
Photographic elements of this invention can differ widely in structure and composition. For example, the photographic elements can vary greatly with regard to the type of support, the number and composition of the image-forming layers, and the number and types of auxiliary layers that are included in the elements. In particular, photographic elements can be still films, motion picture films, x-ray films, graphic arts films, paper prints or microfiche. It is also specifically contemplated to use the conductive layer of the present invention in small format films as described in Research Disclosure, Item 36230 (June 1994). Photographic elements can be either simple black-and-white or monochrome elements or multilayer and/or multicolor elements adapted for use in a negative-positive process or a reversal process. Generally, the photographic element is prepared by coating one side of the film support with one or more layers comprising a dispersion of silver halide crystals in an aqueous solution of gelatin and optionally one or more subbing layers. The coating process can be carried out on a continuously operating coating machine wherein a single layer or a plurality of layers are applied to the support. For multicolor elements, layers can be coated simultaneously on the composite film support as described in U.S. Pat. Nos. 2,761,791 and 3,508,947. Additional useful coating and drying procedures are described in Research Disclosure, Vol. 176, Item 17643 (December, 1978).
Photographic elements protected in accordance with this invention may be derived from silver-halide photographic elements that can be black and white elements (for example, those which yield a silver image or those which yield a neutral tone image from a mixture of dye forming couplers), single color elements or multicolor elements. Multicolor elements typically contain dye image-forming units sensitive to each of the three primary regions of the spectrum. The imaged elements can be imaged elements which are viewed by transmission, such a negative film images, reversal film images and motion-picture prints or they can be imaged elements that are viewed by reflection, such a paper prints. Because of the amount of handling that can occur with paper prints and motion picture prints, they are the preferred imaged photographic elements for use in this invention.
While a primary purpose of applying an overcoat to imaged elements in accordance with this invention is to protect the element from physical damage, application of the overcoat may also protect the image from fading or yellowing. This is particularly true with elements that contain images that are susceptible to fading or yellowing due to the action of oxygen. For example, the fading of dyes derived from pyrazolone and pyrazoloazole couplers is believed to be caused, at least in part, by the presence of oxygen, so that the application of an overcoat which acts as a barrier to the passage of oxygen into the element will reduce such fading.
Photographic elements in which the images to be protected are formed can have the structures and components shown in Research Disclosures 37038 and 38957. Other structures which are useful in this invention are disclosed in commonly owned U.S. Ser. No. 09/299,395, filed Apr. 26, 1999 and U.S. Ser. No. 09/299,548, filed Apr. 26, 1999, incorporated in their entirety by reference. Specific photographic elements can be those shown on pages 96-98 of Research Disclosure 37038 as Color Paper Elements 1 and 2. A typical multicolor photographic element comprises a support bearing a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler.
The photographic element can contain additional layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like. All of these can be coated on a support that can be transparent (for example, a film support) or reflective (for example, a paper support). Photographic elements protected in accordance with the present invention may also include a magnetic recording material as described in Research Disclosure, Item 34390, November 1992, or a transparent magnetic recording layer such as a layer containing magnetic particles on the underside of a transparent support as described in U.S. Pat. Nos. 4,279,945 and 4,302,523.
Suitable silver-halide emulsions and their preparation, as well as methods of chemical and spectral sensitization, are described in Sections I through V of Research Disclosures 37038 and 38957. Others are described in U.S. Ser. No. 09/299,395, filed Apr. 26, 1999 and U.S. Ser. No. 09/299,548, filed Apr. 26, 1999, which are incorporated in their entirety by reference herein. Color materials and development modifiers are described in Sections V through XX of Research Disclosures 37038 and 38957. Vehicles are described in Section II of Research Disclosures 37038 and 38957, and various additives such as brighteners, antifoggants, stabilizers, light absorbing and scattering materials, hardeners, coating aids, plasticizers, lubricants and matting agents are described in Sections VI through X and XI through XIV of Research Disclosures 37038 and 38957. Processing methods and agents are described in Sections XIX and XX of Research Disclosures 37038 and 38957, and methods of exposure are described in Section XVI of Research Disclosures 37038 and 38957.
Photographic elements typically provide the silver halide in the form of an emulsion. Photographic emulsions generally include a vehicle for coating the emulsion as a layer of a photographic element. Useful vehicles include both naturally occurring substances such as proteins, protein derivatives, cellulose derivatives (e.g., cellulose esters), gelatin (e.g., alkali-treated gelatin such as cattle bone or hide gelatin, or acid treated gelatin such as pigskin gelatin), gelatin derivatives (e.g., acetylated gelatin, phthalated gelatin, and the like). Also useful as vehicles or vehicle extenders are hydrophilic water-permeable colloids. These include synthetic polymeric peptizers, carriers, and/or binders such as poly(vinyl alcohol), poly(vinyl lactams), acrylamide polymers, polyvinyl acetals, polymers of alkyl and sulfoalkyl acrylates and methacrylates, hydrolyzed polyvinyl acetates, polyamides, polyvinyl pyridine, methacrylamide copolymers, and the like.
Photographic elements can be imagewise exposed using a variety of techniques. Typically exposure is to light in the visible region of the spectrum, and typically is of a live image through a lens. Exposure can also be to a stored image (such as a computer stored image) by means of light emitting devices (such as LEDs, CRTs, etc.).
Images can be developed in photographic elements in any of a number of well known photographic processes utilizing any of a number of well known processing compositions, described, for example, in T. H. James, editor, The Theory of the Photographic Process, 4th Edition, Macmillan, New York, 1977. In the case of processing a color negative element, the element is treated with a color developer (that is one which will form the colored image dyes with the color couplers), and then with an oxidizer and a solvent to remove silver and silver halide. In the case of processing a color reversal element, the element is first treated with a black and white developer (that is, a developer which does not form colored dyes with the coupler compounds) followed by a treatment to render developable unexposed silver halide (usually chemical or light fogging), followed by treatment with a color developer. Development is followed by bleach-fixing, to remove silver or silver halide, washing and drying.
In one embodiment of a method of using a composition according to the present invention, a photographic element may be provided with a processing-solution-permeable overcoat having the above described composition overlying the silver halide emulsion layer superposed on a support. The photographic element is developed in an alkaline developer solution having a pH greater than 7, preferably greater than 8, more preferably greater than 9. This allows the developer to penetrate the protective coating. After the pH is reduced, for example in a bleach fix solution, the protective overcoat becomes relatively water resistant. The addition of polyvinyl alcohol, according to one embodiment of the present invention, facilitates this method. It has been found the polyvinyl alcohol can provide improved wettability of the surface during processing and, at the same time, allows more of the polyvinyl alcohol to be washed out during the processing, so that the final product is more water resistant. Suitably at least 30%, preferably greater than 50%, more preferably greater than 75% of the original amount of PVA in the overcoat is washed out during processing of the exposed photographic element, such that the final product is depleted in hydrophilic polymer and hence relatively more water resistant. Although the processing-solution-permeable overcoat does not require fusing, optional fusing may improve the water resistance further
The overcoat layer in accordance with this invention is particularly advantageous for use with photographic prints due to superior physical properties including excellent resistance to water-based spills, fingerprinting, fading and yellowing, while providing exceptional transparency and toughness necessary for providing resistance to scratches, abrasion, blocking, and ferrotyping. The present invention also applies to imaged recording elements in which the images, for example, are derived from a pixel-based picture made with a digital still camera. The image can be formed in one or more recording layers, for example as produced using ink-jet printing or electrophotographic printing. Ink-jet printing technology is reviewed in an article titled “Progress and Trends in Ink-Jet Printing Technology” by Hue P. Le in the Journal of Imaging Science and Technology, Volume 42, Number 1 (January/February 1998), pp. 49-61. Essentially, ink droplets, typically in the volume range 1-100 picoliters, are ejected from a printhead to a receiver material on which the image is formed. The ink-jet printhead may be of the continuous or drop-on-demand varieties. Several physical mechanisms for drop ejection are known, but the currently most popular among these are thermal and piezoelectric. In the thermal mechanism, ink in the printhead is heated to form a water vapor bubble that expels one or more ink droplets out of the printhead toward the receiver. Representative thermal ink-jet printheads are described in, for example, U.S. Pat. No. 4,723,129 of Endo et al. (Canon) and U.S. Pat. No. 4,490,728 of Vaught et al. (Hewlett Packard). In the piezoelectric mechanism, one or more droplets are expelled from the printhead by a physical deformation that accompanies a voltage change across a piezoelectric material forming a part of the printhead structure. Representative piezoelectric printheads are described in, for example, U.S. Pat. No. 4,459,601 of Howkins (Exxon) and U.S. Pat. No. 5563634 of Masahiro et al. (Seiko Epson).
The carrier for the ink-jet inks may be comprised solely of water or can be predominantly water mixed with water soluble solvents such as polyhydric alcohols or can be predominantly organic materials such as polyhydric alcohols. The dyes used in such compositions are typically water-soluble direct or acid type dyes. Such liquid ink compositions have been described extensively in the prior art, including, for example, U.S. Pat. No. 4,781,758.
In addition to water and one or more colorants, such as dyes or pigments, an aqueous ink typically contains one or more humectants, which affect ink viscosity and volatility, one or more surfactants, which affect the wetting and penetrating properties of the ink, and a biocide, which extends the useful life of the ink. Aqueous inks may also contain many other ingredients, including metal ion chelating agents, pH buffers, defoamers, and dispersing agents. It is well known to improve the tone scale or bit depth of an image by using more than one ink density for each color. Representative ink-jet inks are described in, for example, U.S. Pat. No. 5,571,850 of Ma et al. (DuPont), U.S. Pat. No. 5, 560,770 of Yatake (Seiko Epson), and U.S. Pat. No. 5,738,716 of Santilli et al. (Eastman Kodak).
Ink-jet media or receivers may be reflective, transparent, or of intermediate transparency (e.g., for day/night display materials). At minimum, an ink-jet receiver includes a support and an ink receiving layer. The simplest ink-jet receiver is plain paper, in which these two functions are combined. As a practical matter, more complex receiver structures are required for improved image quality and physical properties. Specifically formulated ink receiving layers coated on paper or other supports improve color density and dot resolution. Receiver composition and structure may also be modified to improve properties such as wettability, ink absorptivity, drying time, gloss, reduced image artifacts, waterfastness, and light and dark stability. Representative ink-jet receiver structures and compositions are described in, for example, U.S. Pat. No. 4,954,395 of Hasegawa et al. (Canon), U.S. Pat. No. 5,725,961 of Ozawa et al. (Seiko Epson), and U.S. Pat. No. 5,605,750 of Romano et al. (Eastman Kodak).
The use of the present invention in the context of typical recording elements will now be described in more detail. Any support or substrate may be used in a recording element, for example, plain or calendered paper, paper coated with protective polyolefin layers, polymeric films such as poly(cthylene terephthalate), poly(ethylene naphthalate), poly(1,4-cyclohexane dimethylene terephthalate), polyvinyl chloride, polyimide, polycarbonate, polystyrene, or cellulose esters. In particular, polyethylene-coated paper or poly(ethylene terephthalate) is preferred.
The support is suitably of a thickness of from about 50 to about 800 &mgr;m, preferably from about 75 to 500 &mgr;m. Antioxidants, antistatic agents, plasticizers, dyes, pigments and other known additives may be incorporated into the support, if desired.
In order to improve the adhesion of the image-recording layer to the support, the surface of the support may be optionally subjected to a corona-discharge treatment prior to applying the image-recording layer.
Optionally, an additional backing layer or coating may be applied to the backside of a support (i.e., the side of the support opposite the side on which the image-recording layers are coated) for the purposes of improving the machine-handling properties and curl of the recording element, controlling the friction and resistivity thereof, and the like.
Typically, the backing layer may comprise a binder and a filler. Typical fillers include amorphous and crystalline silicas, poly(methyl methacrylate), hollow sphere polystyrene beads, micro crystalline cellulose, zinc oxide, talc, and the like. The filler loaded in the backing layer is generally less than 5 percent by weight of the binder component and the average particle size of the filler material is in the range of 5 to 30 &mgr;m. Typical binders used in the backing layer are polymers such as acrylates, methacrylates, polystyrenes, acrylamides, poly(vinyl chloride)-poly(vinyl acetate) co-polymers, poly(vinyl alcohol), cellulose derivatives, and the like. Additionally, an antistatic agent also can be included in the backing layer to prevent static hindrance of the recording element. Particularly suitable antistatic agents are compounds such as dodecylbenzenesulfonate sodium salt, octyl-sulfonate potassium salt, oligostyrenesulfonate sodium salt, laurylsulfosuccinate sodium salt, and the like. The antistatic agent may be added to the binder composition in an amount of 0.1 to 15 percent by weight, based on the weight of the binder. An image-recording layer may also be coated on the backside, if desired.
Preferably, the support in a recording element is coated with an image forming layer or layers of materials capable of absorbing the carrier and/or dyes in the ink. The thickness of this layer is typically from 5 to 50 micrometers (&mgr;m). The material may include a hydrophilic polymer, including naturally-occuring hydrophilic colloids and gums such as gelatin, albumin, guar, xantham, acacia, chitosan, starches and their derivatives, functionalized proteins, functionalized gums and starches, and cellulose ethers and their derivatives, polyvinyloxazoline and polyvinylmethyloxazoline, polyoxides, polyethers, poly(ethylene imine), poly(acrylic acid), poly(methacrylic acid), n-vinyl amides including polyacrylamide and polyvinylpyrrolidone, and poly(vinyl alcohol), its derivatives and copolymers. Poly(vinyl alcohol) and its derivatives are preferred hydrophilic absorbing materials for use in ink receptive coatings. This layer may also comprise a microporous material. Preferred microporous materials are silica, alumina, or hydrated alumina, boehmite, mica, montmorillonite, kaolite,talc, vermiculite, zeolites, calcium silicate, titanium oxide, barium sulfate, and the like, optionally in combination with a polymeric binder. See, for example, U.S. Pat. No. 5,605,750, incorporated by reference. Many known microporous materials may be employed, including for example, those described in U.S. Patent Nos. 5.032,450; 5,035,886, 5,071,645, and 5,14,438.
For higher quality ink-jet media, a separate upper image-forming layer may be formed above a carrier-absorbing layer. Accordingly, when the ink is ejected from the nozzle of the ink-jet printer in the form of individual droplets, the droplets pass through the upper layer where most of the dyes or pigments in the ink are retained or mordanted while the remaining dyes/pigments and the carrier portion of the ink pass freely through the upper layer to the carrier-absorbing layer where they arc rapidly absorbed, for example, by a hydrophilic polymer and/or microporous material. In this manner, large volumes of ink are quickly absorbed by the recording elements, giving rise to high quality recorded images having excellent optical density and good color gamut.
Image-forming layers in recording elements can also incorporate various known additives, including matting agents such as titanium dioxide, zinc oxide, silica, and polymeric beads such as polystyrene beads for the purposes of contributing to the non-blocking characteristics of the recording elements and to control the smudge resistance thereof; surfactants for improving the aging behavior of the ink-absorbing resin or layer, promoting the absorption and drying of a subsequently applied ink thereto, enhancing the surface uniformity of the ink-receiving layer and adjusting the surface tension of the dried coating; fluorescent dyes; pH controllers; anti-foaming agents; lubricants; preservatives; dye-fixing agents; viscosity modifiers; waterproofing agents; dispersing agents; UV absorbing agents; mordants, and the like.
If desired, in addition to a coating according to the present invention, the recording element can be further coated with an ink-permeable, anti-tack, ink receptive coating, such as, for example, a hydrophilic cellulose derivative such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, calcium carboxymethyl cellulose, methyethyl cellulose, methylhydroxyethyl cellulose, hydroxypropylmethyl cellulose, hydroxybutylmethyl cellulose, ethylhydroxyethyl cellulose, sodium carboxymethylhydroxyethyl cellulose, carboxymethylethyl cellulose, hydroxypropylmethyl cellulose phthalate, hydroxypropylmethyl cellulose acetate succinate, hydroxypropyl cellulose acetate, esters of hydroxyethyl cellulose and diallyldimethyl ammonium chloride, esters of hydroxyethyl cellulose and 2-hydroxypropyltrimethylammonium chloride and esters of hydroxyethyl cellulose and a lauryldimethylammonium substituted epoxide; as well as hydroxyethyl cellulose grafted with alkyl C12-C14 chains.
The present invention is illustrated by the following examples. Unless otherwise indicated, the particle sizes herein are averages as determined by photon correlation spectroscopy.PREPARATIVE EXAMPLES
The preparation of the epoxy particles (Epoxy-1 to Epoxy-7) used to form coated compositions according to the invention are described below.
An oil phase was prepared by dissolving in 42 grams of ethyl acetate, 1.5 grams of Carboset® 526 (an acrylic resin from B. F. Goodrich with an acid number of about 100), 12 grams of EPON™ 1001F (m.p. 60 to 70° C.), 0.12 grams of 2-undecylimidazole, 2 grams of acetone, 2 grams of isopropyl acohol, and 0.24 g of triethyl amine. The prepared oil phase was added to an aqueous phase containing 198 grams of water and 2 grams of Alkanol XC® surfactant under stirring to form an emulsion. The resultant emulsion was then passed three times through a Microfluidizer® mixer. Finally the volatile solvents were removed at room temperature under a stream of nitrogen. The resultant epoxy particle has a polymer (Carboset 526) to epoxy resin of 12.5:87.5 and a mean particle size of about 124.5 nm.
Epoxy-2 was prepared in a similar manner as Epoxy-1 except it has a ratio of polymer (Carboset® 526) to epoxy resin of 1:4 and a mean particle size of about 113 nm.
An oil phase was prepared by dissolving in 125.5 grams of ethyl acetate, 60 grams of EPON™ 1001F (m.p. 60 to 70° C.), 0.6 grams of 2-undecylimidazole, and 14 grams of acetone. The prepared oil phase was added to an aqueous phase containing 768 grams of water, 8 grams of Alkanol® XC surfactant (DuPont Corp.), and 24 grams of poly(vinyl pyrrolidone) (K-30 from International Specialty Products) under stirring to form an emulsion. The resultant emulsion was then passed three times through a Microfluidizer® mixer. Finally the volatile solvents were removed at room temperature under a stream of nitrogen. The resultant epoxy particle has a mean particle size of about 100.4 nm.
Epoxy-4 was prepared in a similar manner as Epoxy-3 except it contains about 12 grams of poly(vinyl pyrrolidone) and has a mean particle size of about 99.3 nm.
Epoxy-5 was prepared in a similar manner as Epoxy-3 except it contains about 6 grams of poly(vinyl pyrrolidone) and has a mean particle size of 110 nm.
Epoxy-6 was prepared in a similar manner as Epoxy-3 except it contains 6 grams of poly(vinyl alcohol) as the polymeric dispersant and has a mean particle size of about 120 nm.
An oil phase was prepared by dissolving in 42 grams of ethyl acetate, 3 grams of Carboset ®525 (an acrylic resin from B. F. Goodrich with an acid number of about 75), 12 grams of EPON™ 1001F (m.p. 60 to 70° C.), 2 grams of Aerosol OT® surfactant, 0.12 grams of 2-undecylimidazole, 2 grams of acetone, 2 grams of isopropyl acohol, and 0.35 g of triethyl amine. The prepared oil phase was added to an aqueous phase containing 200 grams of water under stirring to form an emulsion. The resultant emulsion was then passed three times through a Microfluidizer® mixer. Finally the volatile solvents were removed at room temperature under a stream of nitrogen. The resultant epoxy particle has a ratio of polymer (Carboset® 525) to epoxy resin of 1:4 and a mean particle size of about 92 nm.
The following preparative examples for Com-1 and Com-2 describe the preparation of a polyester polymer particle used in the comparative coating example:
An oil phase was prepared by dissolving in 28 grams of ethyl acetate 12 grams of KAO-C® polymer (a polyester from KAO Corp.). The prepared oil phase was mixed with an aqueous phase containing 129.6 grams of water 1.44 grams of Alkanol XC® surfactant, and 4.8 grams of poly(vinyl pyrrolidone) under vigorous stirring. The resultant emulsion was then passed three times through a Microfluidizer® mixer. Finally the volatile solvents were removed at room temperature under a stream of nitrogen. The resultant polyester particle has a mean particle size of about 140 nm.
An oil phase was prepared by combining 55 grams of a solution in methylene chloride containing 20% LF200® (a fluoropolymer resin from Zeneca Resins) and 20 grams of a solution in ethyl acetate containing 15% Carboset® 526 polymer. The prepared oil phase was then combined with 5 grams of isopropyl alcohol and 0.4 grams of triethyl amine. The oil phase was mixed with an aqueous phase containing about 3 grams of Alkanol XC® surfactant and 290 grams of water under vigorous stirring. The resultant emulsion was then passed three times through a Microfluidiser® mixer. The volatile organic solvent was removed. The resultant polymer particle has a mean particle size of about 180 nm.
(1) Poly(vinyl alcohol) (PVA) was obtained from Aldrich Chem. Co., Cat. No. 36,062-7.
(2) Poly(vinylpyrrolidone) K-30 was obtained from International Specialty Products.Examples 1 Through 7
This Example illustrates the water-resistance of coatings according to the present invention. A series of coating examples were prepared as follows: A photographic paper support was used having a resin coated sublayer 1 (Titanox® and optical brightener in polyethylene) on one side and a resin coated sublayer 2 on the other side. The support was coated on the sublayer 1 side a gelatin layer have a dry coverage of about 3 grams/m2. An overcoat layer was applied over the gelatin layer containing about 150 mg/m2 MT-200 lubricant (Michelman Inc.), 50 mg/m2 of Surfactant Olin® 10G (Olin Corp.), and various ingredients listed in Table 1 below. The gelatin was hardened with HAR-1.TABLE 1 Polymer Particle Poly(vinyl Coating Coverage pyrrolidone) Examples Gelatin (mg/m2) ID (mg/m2) (mg/m2) Example 1 1300 — — — (Comparative) Example 2 — Epoxy-2 1134 — (Invention) Example 3 195 Epoxy-2 1134 — (Invention) Example 4 240 Epoxy-2 1400 — (Invention) Example 5 195 Epoxy-1 1134 — (Invention) Example 6 240 Epoxy-1 1400 — (Invention) Example 7 — Epoxy-1 1134 195 (invention)
The above coating examples were tested for their resistance to water and a photographic paper developer by measuring the time it takes for the coating to reach 80% of its equilibrium swelling value in 0.1N NaCl aqueous solution and in RA-4 developer. The results are listed in Table 2 below.TABLE 2 Coating Developer Swelling Examples (Second) Water Swelling (Second) Example 1 6 6 (Comparative) Example 2 15 198 (Invention) Example 3 13.5 44 (Invention) Example 4 16.5 62 (Invention) Example 5 12 96 (Invention) Example 6 18 72 (Invention) Example 7 13.5 116 (invention)
The results in Table 2 above demonstrate that the coating examples prepared in accordance with the invention show excellent resistance to water penetration but have no significant effect on swelling by the photographic developer. Therefore the coating compositions of the invention are useful for forming protective overcoats for photographic elements and ink jet ink recording elements since those image elements require both developability by photographic developers or ink jet inks and resistance to water damage.Examples 8 Thorugh 21
This Example illustrates the stain-resistance of coatings according to the present invention. A series coating examples were prepared as follows: A photographic paper support was used having a resin coated sublayer 1 (Titanox® and optical brightener in polyethylene) on one side and a resin coated sublayer 2 on the other side. The support was coated on the sublayer 1 side with a gelatin layer have a dry coverage of about 3 grams/m2. An overcoat layer was applied over the gelatin layer containing about 150 mg/m2 MT-200® lubricant (Michelman Inc.), 50 mg/m2 of Surfactant Olin®10G (Olin Corp.), and various ingredients listed in Table 3. The gelatin was hardened with HAR-1.TABLE 3 Polymer Particle Poly(vinyl Gelatin Coverage pyrrolidone) Coating Examples (mg/m2) ID (mg/m2) (mg/m2) Example 8 1300 — — — (Comparative) Example 9 — Epoxy-2 1134 — (Invention) Example 10 195 Epoxy-2 1134 — (Invention) Example 11 240 Epoxy-2 1400 — (Invention) Example 12 — Epoxy-1 1134 — (Invention) Example 13 240 Epoxy-1 1400 — (Invention) Example 14 — Epoxy-1 1134 195 (invention) Example 15 — Epoxy-3 1134 470 (Invention) Example 16 240 Epoxy-3 1400 590 (Invention) Example 17 195 Epoxy-4 1134 240 (Invention) Example 18 240 Epoxy-4 1400 280 (Invention) Example 19 240 Epoxy-7 1400 — (Invention) Example 20 240 Com-1 1400 590 (Comparative) Example 21 240 Com-2 1134 — (Comparative)
The coatings processed through Kodak RA4 process. After the coatings were dried, they were subjected to further heat treatment between heated rollers, at least one of which was heated at a temperature of 300° F., at a speed of 60 inches per minute. The dye stain resistance was measured using a Ponceau Red dye solution prepared by dissolving 1 gram dye in 1000 grams mixture of acetic acid and water (5 parts: 95 parts). A drop of the dye solution was spread on the coating surface. The covered area had a diameter of about 2 cm. After 5 minutes the dye solution was rubbed off using a piece of paper towel. The samples were inspected visually and the stain resistance was measured by the amount of residual red color on the surface against the following scale:Value Amount of residual color A No residual color B Trace amount of residual color C Very light residual color D Light residual color E Very heavy residual color
The testing results are listed in Table 4 below.TABLE 4 Dye Stain Coating Examples Resistance Example 8 E (Comparative) Example 9 B (Invention) Example 10 B (Invention) Example 11 A (Invention) Example 12 A (Invention) Example 13 B (Invention) Example 14 A (invention) Example 15 A (Invention) Example 16 B (Invention) Example 17 B (Invention) Example 18 A (Invention) Example 19 B (Invention) Example 20 E (Comparative) Example 21 D (Comparative)
The results in Table 4 demonstrate that the coating examples prepared in according to the invention have excellent stain resistance. Comparative coating example 21 contains a fluopolymer particle and it shows only marginal improvement on dye stain. Comparative coating example 20 contains a polyester particle and it does not show any improvement on dye stain.Examples 22 Through 26
Photographic elements were prepared by coating in sequence blue-light sensitive layer, interlayer, green-light sensitive layer, UV layer, red-light sensitive layer, UV layer and overcoat on photographic paper support. The components in each individual layer is described below. The overcoat layer for Examples 23 through contains about 150 mg/m2 MT-200® lubricant (Michelman Inc.), 50 mg/m2 of Surfactant Olin® 10G (Olin Corp.), and various ingredients listed in Table 5. Comparative Example 22 has an overcoat containing 600 mg/m2 of gelatin and 150 mg/m2 of colloidal silica (Ludox® AM). Gelatin was hardened using HAR-1.UV 12.11 UV-1 2.13 UV-2 3.57 SCV-1 2.37 S-1 2.37 S-2 47.5 Gelatin Cyan 18.1 Red light sensitive AgX 39.31 C-1 38.52 S-2 3.22 S-3 25.31 UV-1 129.0 Gelatin UV 17.43 UV-1 3.07 UV-2 5.14 SCV-1 3.41 S-1 3.41 S-2 68.4 Gelatin Magenta 7.70 Green-light sensitive AgX 1.11 KCL 29.5 C-2 8.26 S-2 3.54 S-4 17.7 ST-1 2.01 ST-2 57.0 ST-3 0.05 FOG-1 0.285 Nitric Acid 117.0 Gelatin Layer Laydown (mg/sq. ft.) IL 6.12 SCV-1 18.4 S-2 6.025 3,5-Disulfocatechol disodium salt 0.524 Nitric Acid 0.18 SURF-1 70.0 Gelatin Yellow 24.0 Blue-light sensitive AgX 45.0 C-3 45.0 P-1 20.3 S-2 0.88 SCV-2 141.8 Gelatin
Photographic paper support
sublayer 1: resin coat (Titanox and optic brightener in polyethylene)
sublayer 2: paper
sublayer 3: resin coat (polyethylene)C-1 Butanamide 2-[2,4-bis(1,1-dimethylpropyl)phenoxy]-N-(3,5- dichloro-4-ethyl-2-hydroxyphenyl) C-2 C-3 FOG-1 HAR-1 P-1 S-1 1,4-Cyclohexylenedimethylene bis(2-ethylhexaneoate) S-2 S-3 2-(2-Butoxyethoxy)ethyl acetate S-4 Di-undecylphthalate SCV-1 SCV-2 benzenesulfonic acid 2,5-dihydroxy-4-(1-methylheptadecyl)- mono-potassium salt ST-1 ST-2 ST-3 SURF-1 SURF-2 C8F17SO3N(C2H5)4 UV-1 UV-2 TABLE 5 Polymer Particle Poly(vinyl Gelatin Coverage alcohol) Coating Examples (mg/m2) ID (mg/m2) (mg/m2) Example 23 240 Epoxy-1 1400 — (Invention) Example 24 275 Epoxy-1 1600 — (Invention) Example 25 275 Epoxy-1 1600 100 (invention) Example 26 367 Epoxy-1 1600 — (Invention)
The coatings processed through Kodak RA4 process. After the coatings were dried, they were subjected to further heat treatment between heated rollers, at least one of which was heated at a temperature of 300° F., at a speed of 60 inches per minute. The dye stain resistance was measured using a Ponceau Red dye solution as before. The results are listed in Table 6.TABLE 6 Dye Stain Coating Examples Resistance Example 22 E (Comparative) Example 23 A (Invention) Example 24 A (Invention) Example 25 B (Invention) Example 26 A (Invention)
Results in Table 6 demonstrate that the photographic elements prepared in according to the present invention have excellent dye stain resistance.
The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
1. A method of making an imaged print having a water-resistant overcoat, which method comprises in order the following:
- (a) providing an imaging element comprising a support, at least one image-receiving layer, and overlying the at least one image-receiving layer at least one layer having a laydown of at least 0.54 g/m 2 (50 mg/ft 2 ) of an overcoat composition comprising water-dispersible particles having an average particle size of from 0.01 to 5 microns and a Tg of greater than 20° C., which particles comprise an epoxy material, having on average at least 1.5 epoxy groups per molecule, and a hydrophilic polymer; and
- (b) forming an dye or pigment based pictorial image in the image-receiving layer using ink jet or a developing agent, and
- (c) fusing the overcoat at a temperature over 100° C. to render the overcoat water-resistant in the final product.
2. The method of claim 1, wherein the overcoat further comprises a polymer having an acid number between 30 and 250, wherein the acid groups carried by the polymer have been neutralized by a base to a degree of neutralization of 50 to 90%, and wherein at least a portion of the epoxy groups react with the acid groups of the polymer during fusing.
3. The method of claim 1 wherein the hydrophilic polymer is gelatin or poly(vinylpyrrolidone).
4. The method of claim 1 wherein the epoxy material is selected from the group consisting of epoxy resin is a diglycidyl ether of a dihydric phenol.
5. The method of claim 1 wherein the image receiving layer comprises a silver-halide emulsion.
6. A method of making a photographic print having a water-resistant overcoat, which method comprises in order:
- (a) providing a photographic element comprising a support, at least one image-receiving silver-halide emulsion layer, and overlying the at least one emulsion layer at least one layer having a laydown of at least 0.54 g/m 2 (50 mg/ft 2 ) of an overcoat composition comprising water-dispersible latex particles having an average particle size of from 0.01 to 0.5 microns and a Tg of greater than 20° C., which particles comprise an epoxy material, having on average at least 1.5 epoxy groups per molecule, and a hydrophilic polymer;
- (b) image-wise exposing the photographic element to light;
- (c) forming an dye-based pictorial image in the image-receiving layer using a developing agent, and
- (d) fusing the overcoat at a temperature over 100° C. to render the overcoat water-resistant in the final product.
7. An imaging element having a nascent water-resistant protective overcoat thereon, comprising the following:
- (a) a support;
- (b) at least one image-receiving layer for carrying a dye or pigment-based pictorial image; and
- (c) overlying the at least one image-receiving layer at least one layer having a laydown of at least 0.54 g/m 2 (50 mg/ft 2 ) of a coating composition comprising
- (i) water-dispersible particles having an average particle size of from 0.01 to 5 microns and a Tg of greater than 20° C., which particles comprise an epoxy-containing material containing on average at least 1.5 epoxy groups per molecule, and
- (ii) a hydrophilic binder selected from the group consisting of gelatin, polyvinylpyrrolidone, and combinations thereof.
8. The imaging element of claim 7 wherein the epoxy material is selected from the group consisting of epoxy resin is a diglycidyl ether of a dihydric phenol.
9. The imaging element of claim 7 wherein the image receiving layer comprises a silver-halide emulsion.
10. The imaging element of claim 7 wherein the overcoat further comprises a polymer having an acid number between 30 and 250, wherein the acid groups carried by the polymer have been neutralized by a base to a degree of neutralization of 50 to 95%.
11. The imaging element of claim 10 wherein the polymer comprises a repeat unit derived from a monomer selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid.
12. The imaging element of claim 7 wherein the support comprises polymeric films, papers or glass.
13. The imaging element of claim 7 wherein the overcoat composition further comprises UV absorbers, surfactants, emulsifiers, coating aids, lubricants, matte particles, rheology modifiers, crosslinking agents, antifoggants, inorganic fillers, pigments, magnetic particles and/or biocides.
14. An imaged element having a water-resistant protective overcoat thereon, comprising the following:
- (a) a support;
- (b) at least one image-receiving layer for carrying a dye or pigment-based pictorial image; and
- (c) overlying the at least one image-receiving layer a protective overcoat having a laydown of at least 0.54 g/m 2 (50 mg/ft 2 ) and comprising the fused reaction product of an epoxy material having an average particle size of from 0.01 to 5 microns and a Tg of greater than 20° C., containing on average at least 1.5 epoxy groups per molecule, and a polymer having an acid number between 30 and 250, wherein the acid groups carried by the polymer have been neutralized by a base to a degree of neutralization of 50 to 95%, said overcoat further comprising a binder comprising gelatin and/or poly(vinylpyrrolidone).
15. The imaging element of claim 14 wherein the image is based on ink-jet.
16. The imaging element of claim 15 wherein the image is based on the reaction of a coupler with a developing agent in the presence of silver-halide emulsion.
|4554235||November 19, 1985||Adair et al.|
|4797353||January 10, 1989||Yamada et al.|
|5853926||December 29, 1998||Bohan et al.|
|5856051||January 5, 1999||Yau et al.|
|6153363||November 28, 2000||Nair et al.|
|6187517||February 13, 2001||Whitesides et al.|
|6190843||February 20, 2001||Yau et al.|
|6194130||February 27, 2001||Nair et al.|
|6232049||May 15, 2001||Nair et al.|
Filed: Oct 30, 2000
Date of Patent: Feb 12, 2002
Assignee: Eastman Kodak Company (Rochester, NY)
Inventors: Yongcai Wang (Webster, NY), Kevin M. O'Connor (Webster, NY), Tiecheng A. Qiao (Webster, NY)
Primary Examiner: Richard L. Schilling
Attorney, Agent or Law Firm: Chris P. Konkol
Application Number: 09/699,815
International Classification: G03C/1106; G03C/1108; G03C/176; G03C/526; B41J/3407;

domain: chemistry


Who invented the electric guitar and when?
The earliest electric guitars were made in the 1920s and 1930s, but these were very primitive prototypes of the modern solid- body electrical guitar. The very first electrified guitar was said to have been invented by Paul H. Tutmarc.
Who was the first person to play an electric guitar?
Invented in 1932, the electric guitar was adopted by jazz guitar players, who wanted to play single-note guitar solos in large big band ensembles. Early proponents of the electric guitar on record include Les Paul , Lonnie Johnson, Sister Rosetta Tharpe, T-Bone Walker, and Charlie Christian .
When did Les Paul invent the electric guitar?
Who invented the first affordable electric guitar?
“It made the small combo possible, where four guys could create as much noise as a 15-piece big band. “Leo made the electric guitar useful, affordable and commercially viable, something nobody had ever done before,” says Smith, who’s writing a book about Fender. “He’s the Thomas Edison of guitars .”
Is Guitar losing popularity?
The numbers are pretty shocking. In just the past decade, electric guitar sales have dropped by a third, from 1.5 million to a new average of just over 1 million. there’s almost a popular sense that musicians have taken guitar music as far as it can go while electronic composition provides limitless options.
What should my first electric guitar be?
While there are slightly cheaper models in their catalogue, the Squier Classic Vibe ’50s Stratocaster takes our vote as the best beginner’s electric guitar . It’s well-made, so able to withstand your formative playing years, and is cost-effective too. Both important ingredients when choosing your first electric .
How long does an electric guitar last?
The roughest estimation would be around 10 years for a cheap acousticclassical guitar. On the other hand, even cheap electric guitars will be able to last a lot longer, 20-30 years . Of course, if we talk about expensive models, both acoustic and electric guitars will be able to last you for a lifetime.
What electric guitar should I buy?
The best electric guitars to buy now Fender Player Stratocaster. Fender’s entry-level Strat delivers serious value for money. PRS SE Custom 24. Gretsch G2622 Streamliner. PRS S2 Standard Singlecut Satin. Fender Vintera ’60s Telecaster Bigsby. Yamaha Pacifica 112V. Ibanez RG550. Epiphone Les Paul Standard PlusTop Pro.
Did a black man invent the guitar?
Although guitars have existed in Africa for millenniums, Robert F. Flemming, Jr., the Black American, is credited as the first man to have invented the modern guitar on the 3rd of March 1886.
Why are Les Pauls so expensive?
Les Pauls are generally more expensive than other guitars due to the construction techniques: set neck, binding, wood species, labor etc. To put things into perspective, electric guitars are fairly inexpensive compared to other instruments. If you want a Les Paul and don’t want to spend a lot, get a Studio.
Who was Les Paul’s wife?
Mary Ford m. 1949–1964 Virginia Webb m. 1938–1949
Is Mary Ford still alive?
Who built the first guitar?
George Beauchamp Adolph Rickenbacker
Which country invented the electric guitar?
What is the single most important instrument in rock n roll?


Policy, Science, and the Environment
Week 16: December 6, 2011
Course Wrap Up/Grad Student panel
Lynn, Jr., L. 2001. The making and analysis of public policy: a perspective on the role of social science, Chapter 8, pp. 187-218 in D. L. Featherman and M. A, Vonovskis (eds.) Social Science and Policy-Making: A Search for Relevance in the Twentieth Century (University of Michigan Press).
Brunner, R. D. 1991. The policy movement as a policy problem, Policy Sciences 24:65-98.
Wildavsky, A. 1985. The once and future school of public policy, The Public Interest 79:25-41.
Clark, T., 2002. The Policy Process: A practical guide for natural resource professionals, Yale University Press.
Schelenberger, M. and T. Nordhaus, 2004. The Death of Environmentalism, The Breakthrough Institute.
ENVS Grad Student panel
Fisher, E., 2005. Lessons learned from the Ethical, Legal and Social Implications program (ELSI): Planning societal implications research for the National Nanotechnology Program, Technology in Society, 27:321-328.
Gent C.E., 2000. Needle exchange policy adoption in American cities: Why not? Policy Sciences, 33:125-153.
Logar, N. And L.K. Pollack, 2005. Transgenic fish: is a new policy framework necessary for a new technology? Environmental Science & Policy 8:17-27.
Vogel, J. M., 2004. Tunnel vision: The regulation of endocrine disruptors, Policy Sciences, 37:277-303.


text:
Darling Darling Kannada Movie Song
Write about topics that interest you - anything from movies to cricket, gadgets to startups. Sri Venkateshwara Creations Reliance Movies. Chris Stapleton feels honoured to sing Randy Newman's song. Quirky songs crooned by the legendary singer in Telugu cinema. His attempts are always thwarted by her brother.
Hanumantha Rao, on Viswanath's behalf, negotiates with his father for a reconciliation. You can update your channel preference from the Settings menu in the header menu. Rimi Tomy has a gala time in Nepal. Participate in Write India Junior.
Narayana son, who gatecrashes into the game as he is cheered by Nandini. He sends his men to kill her but Prabha manages to stop them and save Nandini. You can change your city from here. Youth awareness vital for change. One of his customers is rich in beauty and talent.
Priyanka Chopra stuns in black thigh-high slit dress. They finally get married and live a happy life.
Nisha's father too realizes the truth that the story Prabha had said was a lie, and tries to kill him. Now Gubbi is given offer for marriage of his sister Poorni by Bhavani.
Darling Telugu Movie Songs Lyrics
To verify, just follow the link in the message. We serve personalized stories based on the selected city.
To reach their professional goals, Vishwanath and Nandini travel to Switzerland, while Hanumantha Rao becomes a criminal lawyer and settles in India. Mumbaikars celebrate World Laughter Day.
Both Rishi and Prabha vie with each other to impress Nandini, leading to a cold war between them. Narayana playing supporting roles.
Nature's offerings for your skin. Mumbaikars celebrate World Bicycle Day.
Cricketer Ishan Kishan gets a complicated tattoo. Prabha decides not to reveal his love for Nandini and makes up his mind to leave. Gubbi has to eradicate Santhya. As a result, he is ousted by his father. The eternal love facing ordeals from two sides handled by the lovers is the crux of this film.
Facebook Twitter Pintrest. Miss India state winners arrive in Mumbai. Now Playing Kartik Aaryan sports a new look.
We have sent you a verification email. Popular Australian model found dead in her Sydney home.
Let's work together to keep the conversation civil. Even Viswanath's father feels emotional about it, forgives his son and allows Nandini to marry Prabha. Later the audio was released by all the directors and the first copy of it was received by all heroes who attended the function.
The second film of director Santhu concentrates more on the commercial elements like dance, action, thrill, comedy and suspense. Inspector Tawde plans to ruin Dhanak and Raghu's life. But to save his father's reputation, he doesn't reveal his love to her and leaves the place, leaving Nandini heartbroken. Now Playing Here's what Salman feels about his family. Miss India Telangana registrations.
Bollywood stars reveal their beauty secrets. Adi Lokesh, Ninasam Ashwath, Avinash given able support.
Kannada Dj Song
Guddan Tumse Na Ho Payega completes episodes. City cyclists go on an early morning fitness ride.
Anuradha Pal talks about her love for the tabla. Janhvi Kapoor gets obsessed with her yellow sling bag! The barricade is Poorni brother Bhavani an underworld don.
The protagonist Sathya Yogish a tattoo artist running a small shop is very popular for his drawings among the girls. Ananya Pandey breaks silence on dating Kartik Aaryan. When Mumbaikars got creative with fluid art! It is problem on the lovers.
Mika returns to Kannada films with the peppy title song Darling Darling, which is a song where mass meets romance. Darling is a Indian Telugu-language romantic comedy - family drama film, aankh bhar aayi hai dil ghabraya hai mp3 directed by A. Darling character suits the image of Loose Madha Yogish. The movie starts in the late s when a group of friends celebrate their farewell party.
Hanumantha Rao reminds him of the condition but Viswanath says no and reminds him of their friendship for helping each other. Now Playing PeeCee on criticism over age gap with Nick. Does this Kathakali painting follow you? Tushar Kalia on the unique format of his dance show.
- Fe sizer
- Chair cad block free download
- Full text translator free download
- Smile charlie chaplin free download
- Xv file player free download
- Game for girl fashion free download
- Patrician 2 full version
- Adobe reader 9.1
- Cdma workshop cracked free download
- Police force 2 pc game free download
- Aol9 6 free download
- Sygic india gps navigation for android
- Mmpds free download
- Kantoi mp3 free download
- 30 seconds to mars a beautiful lie album

domain: entertainment


Grab your Solar Powered Ultrasonic Animal Repeller while the 50% OFF DISCOUNT is on. Once we sell 200 units, price will increase back to full retail price.
Powered by an amorphous solar panel - solar power is economical and environmentally friendly. Solar power means this product requires no cords or cables - simply put in place, and wait for it to charge.
PIR (passive infra-red sensor) can detect motion within a 30 ft (9.14m) radius.
Device only activates when motion sensor is triggered, making the most of its power supply is effective in repelling various pests - for example, cats, dogs, foxes, and rodents.
Ultrasonic Frequency: 18-40KHz
Waterproof rating: IPX4
Loudspeaker: This product can be issued with high frequency ultrasound to drive away the animal.
PIR motion detector: This is a pyroelectric infrared sensor, when there is a moving animal in the detection range, it will detect, while giving the processor a signal to let the device start working, issue acoustic frequency to drive the animal and the white LED indication The lights also flicker.
Red LED: Sensing to animal red LED is on, indicating the working status of the device.
White LED flash flash: induction to the animal, white LED flash light began to work, each flashing 3, the flash interval of 1.5 seconds, has continued to cycle until the animals leave the protected area for 15 seconds, the device stops working, into standby.
Strong flash white LED for some animals such as bird mouse cat and other effects better.
Ultrasonic frequency conversion: Ultrasonic frequency conversion frequency band: 25kHz, 34kHz, 43kHz, 52kHz, 61kHz, each band work 2.5 seconds, so reciprocating cycle.
We have two modes of this products: one is with light repeller, the other one is not. Please choose the right one according to your needs
Allow the Animal Repeller to operate continuously for best results.
Do not immerse repeller in water.
Do not cover-up the PIR sensor
To clean the repeller, use a damp-soft cloth and mild soap with water.
Do not use harsh chemicals or abrasive cleaning agents that may damage the repeller.
The real color of the item may be slightly different from the pictures shown on website caused by many factors such as brightness of your monitor and light brightness.
At Trend Delivery, we strive to offer the top and high-quality products in the world.
Your Satisfaction is our Top Priority.
We will provide outstanding customer service to assist you as we highly value our customer satisfaction with absolutely Zero Risk.


text:
In the chaos of our modern lives, where stress and anxiety seem to be constant companions, the soothing touch of a therapeutic massage offers a much-needed escape into a world of relaxation and rejuvenation. The healing power of massage has been acknowledged for centuries, and its benefits extend far beyond mere physical relaxation. It is a journey to total relaxation—a holistic experience that heals the body, calms the mind and nurtures the soul.
Ancient Roots, Modern Benefits
Massage is not a recent phenomenon but a practice that dates back thousands of years. Its roots can be traced to various cultures, from ancient Egypt and Greece to China and India. In the present day, massage therapy has evolved into a multifaceted field with a wide range of techniques and modalities, each designed to address specific needs and promote overall well-being.
One of the most immediate and tangible benefits of massage is its ability to alleviate physical discomfort. Whether it's a sore back, stiff neck or tight muscles from a long day at work, the skilled hands of a masseuse or masseur can work wonders. The application of pressure, kneading and stretching techniques helps release tension, improve circulation and reduce muscle stiffness.
Stress Reduction and Mental Calm
Beyond the physical aspect, massage therapy provides profound stress reduction and mental relaxation. Stress is a prevalent issue in today's fast-paced world, and it takes a toll on our bodies and minds. A therapeutic massage at salons like utopiabeautique.com allows the recipient to unwind, release pent-up stress and enter a state of deep relaxation. This not only feels pleasant but also has significant mental and emotional benefits.
Promoting Sleep Quality
Many individuals struggle with sleep-related issues, whether it's insomnia, restless nights or frequent awakenings. Massage can be a natural remedy for improving sleep quality. The relaxation achieved during a massage can help balance sleep patterns and promote more restful slumber. A regular massage regimen may contribute to better sleep and overall well-being.
Pain Management and Rehabilitation
For those dealing with chronic pain conditions, injuries or post-surgery recovery, massage therapy can be an integral part of their healing journey. Therapeutic techniques can address pain points, aid in injury recovery and assist in the rehabilitation process. It can reduce discomfort and improve mobility, enhancing the quality of life for those in pain.
Regular massages stimulate the lymphatic system, which helps to eliminate waste products from the body. This enhanced lymphatic flow helps strengthen the immune system, making the body more resilient against illnesses.
The benefits of massage extend to emotional well-being as well. The power of human touch and the caring environment of a massage session create a sense of connection and comfort. This emotional support can ease anxiety and depressive symptoms, promoting a sense of emotional balance and inner peace.
In a world filled with the relentless pace of daily life and the pressures that accompany it, taking time for a massage can be a transformative experience. The healing power of massage is not just a luxury but an essential component of a balanced and healthy life. It's a journey that everyone should experience to unlock the profound benefits it offers for total relaxation and well-being.

domain: health


text:
Dongchimi (Korean Radish Water Kimchi) Recipe
I cannot say enough about how much I absolutely love… Dongchimi. The refreshing broth and the crunchy radish moo… Yum!
Bill will do a post on it soon, but we’re currently watching the drama Kimchi Family or Fermentation Family (available on DramaFever – Kimchi Family). This drama is probably one of my very favorite dramas in the recent years. We’ve watched half of the episodes so far, and each episode shows such beautiful and delicious looking kimchi and food that we get really hungry. And I just get this passionate desire to go and make kimchi. After watching an episode a couple of weeks ago, I ran out to make Dongchimi, so I hope you enjoy the recipe!
Dongchimi has always been my favorite kimchi. Dongchimi literally means kimchi for the winter, and Koreans love eating Dongchimi with steamy, hot dishes during the winter. But Dongchimi is eaten all around the year, including summer, when Koreans like to make noodles with the Dongchimi broth – which we call Neungmyun (cold noodles).
Unlike the red, spicy kimchis that you often see in Korean meals, Dongchimi is a water-based, non-spicy kimchi that has an amazing, refreshing broth. Like any other kimchi, Dongchimi is also a very healthy food – I don’t need to go into how probiotic food is so amazingly good for you!
Dongchimi is much easier to make than regular kimchi. It’s an easy recipe that gives great results for newbies, and it is a very satisfying side dish for any steamy and hot or hearty Korean meal. Again, it’s great as Neungmyun (cold noodles) broth as well. 🙂
Dongchimi (Korean Radish Water Kimchi) Recipe
5 medium Korean moo/radish/daikon (make sure it’s the Korean radish, the other kinds will taste totally different!)
3/4-1 cup coarse sea salt to cover the moo/radish overnight
1 big Korean pear, cubed (make sure it’s Korean pear for this recipe!)
1 big or 2 small red apples, cubed
1 cup whole garlic cloves
20 whole green onions salted and tied into knots
5-7 ginger pieces, cubed (garlic clove size)
8-10 mix of red & green hot peppers (accordingly to your liking)
1/16 cup pepper seeds wrapped and tied in cheese cloth (optional, only if you want to have some more heat in the kimchi)
sea salted water (18 cups of water with 2/3 cup sea salt)
1. Clean and peel the bad/ugly areas of the moo/radish peel. Don’t peel everything out, as the peel of the moo will make the broth yummier!
2. Slice the moo into quarters, rub with salt and let it sit overnight.
3. In the morning, wash the moo and salt the green onions for 30 minutes.
4. Meanwhile, prepare the apple, pear, garlic cloves, ginger chops, whole peppers, and pepper seeds (if you are using them). Put them all in a glass jar.
5. Check if the green onions have wilted. If they have, wrap them into knots (they don’t have to be too pretty), and put them in the glass jar.
6. Put in the salted moo/radish. You should have all the ingredients in the jar now.
7. Make your sea salt water and add it into the jar. Cover up the ingredients completely. You are done!!!!
8. Put it in your fridge to ferment for at least a week or so. You can start eating as soon as you make it but really it won’t be as yummy before it has time to ferment.
9. If you let it sit for around 2 weeks or so, the Dongchimi will have a much stronger, refreshing kimchi broth taste – in a really awesome probiotics kind of way! 🙂
Salt the radish moo really well. Be sure to sprinkle generous amounts of salt!
Salted radish moo is ready for you in the morning. Wash them!
Cut the apples and Korean pears into cubes like this. Cut the ginger into garlic size cubes as well!
Salt the green onions so they are wilted enough to make knots!
Wrap them into large knots!
If all the ingredients are ready, put them all into the jar. The peppers just need to washed and put in whole.
Put the moo radish in as well and add the sea salted water to cover up all the ingredients.
All ready to be fermented now! Keep it out for a day (you want to have it the jar lid slightly open to let air in for fermentation). Then place in your fridge to ferment for at least a week or more. If you can let it ferment longer, the better.
You can really start eating as soon as you make it but waiting until it ferments really pays of. The waiting is very difficult for me. I can’t wait to eat Dongchimi, so I always end up eating some pretty early. But you can clearly taste how different the broth and radish moo taste after letting it ferment for a couple of weeks. So please be patient! 😉
Yumm… the refreshing broth and the crunchy radish moo. Enjoy!

domain: food