text:
Publication number | US6645690 B2 |
Publication type | Grant |
Application number | US 10/037,050 |
Publication date | Nov 11, 2003 |
Filing date | Dec 21, 2001 |
Priority date | Dec 21, 2001 |
Fee status | Lapsed |
Also published as | CN1427297A, US20030162122 |
Publication number | 037050, 10037050, US 6645690 B2, US 6645690B2, US-B2-6645690, US6645690 B2, US6645690B2 |
Inventors | Mridula Nair, Robert P. Bourdelais, Jehuda Greener |
Original Assignee | Eastman Kodak Company |
Export Citation | BiBTeX, EndNote, RefMan |
Patent Citations (13), Referenced by (6), Classifications (23), Legal Events (5) | |
External Links: USPTO, USPTO Assignment, Espacenet | |
The invention relates to controlling the curl of gelatin containing photographic elements at low relative humidities and high temperatures through the use of a flexibilizer agent. In a preferred form it relates to the use of silver halide pressure sensitive label for the printing of text, graphics and images applied to packaging material having good curl resistance at low relative humidities and high temperatures.
Pressure sensitive labels are applied to packages to build brand awareness, describe the contents of the package, convey a quality message regarding the contents of a package and supply consumer information such as directions on product use, or an ingredient listing of the contents. Printing on the pressure sensitive label is typically printed by gravure printing or flexography is applied to the package. The three types of information applied to a pressure sensitive label are text, graphic and images. Some packages only require one type of information while other packages require more than one type of information.
Prior art labels that are applied to packages consist of a face stock material, a pressure sensitive adhesive and a liner. The label substrate consisting of the face stock, pressure sensitive adhesive and liner are typically laminated and then printed utilizing a variety of non-photographic printing methods. After printing, the labels are generally protected by an over laminate material or a protective coating. The completed label consisting of a protection layer, printed information, base stock and pressure sensitive adhesive is applied to packages utilizing high speed labeling equipment.
Flexography is an offset letterpress technique where the printing plates are made from rubber or photopolymers. The printing on pressure sensitive label is accomplished by the transfer of ink from the raised surface of the printing plate to the surface of the material being printed. The rotogravure method of printing uses a print cylinder with thousands of tiny cells which are below the surface of the printing cylinder. The ink is transferred from the cells when the print cylinder is brought into contact with the pressure sensitive label at the impression roll. Printing inks for flexography or rotogravure include solvent based inks, water based inks and radiation cured inks. While rotogravure and flexography printing do provide acceptable image quality, these two printing methods require expensive and time consuming preparation of print cylinders or printing plates which make printing jobs of less than 100,000 units expensive as the set up cost and the cost of the cylinders or printing plates is typically depreciated over the size of the print job.
Recently, digital printing has become a viable method for the printing of information on packages. The term digital printing refers to the electronic digital characters or electronic digital images that can be printed by an electronic output device capable of translating digital information. The two main digital printing technologies are ink jet and electrophotography.
The introduction of piezo impulse drop-on-demand (DOD) and thermal DOD ink jet printers in the early 1980's provided ink jet printing systems. These early printers were very slow, and the ink jet nozzles often clogged. In the 1990's Hewlett Packard introduced the first monochrome inkjet printer, and, shortly thereafter, the introduction of color, wide format ink jet printers enabled businesses to enter the graphic arts market. Today, a number of different ink jet technologies are being used for packaging, desktop, industrial, commercial, photographic, and textile applications.
In piezo technology, a piezo crystal is electrically stimulated to create pressure waves, which eject ink from the ink chamber. The ink can be electrically charged and deflected in a potential field, allowing the different characters to be created. More recent developments have introduced DOD multiple jets that utilize conductive piezo ceramic material, which, when charged, increases the pressure in the channel and forces a drop of ink from the end of the nozzle. This allows for very small droplets of ink to form and be delivered at high speed at very high resolution, approximately 1,000 dpi printing.
Until recently, the use of color pigments in jet inks was uncommon. However, this is changing rapidly. Submicron pigments were developed in Japan for ink jet applications. Use of pigments allows for more temperature resistant inks required for thermal ink jet printers and laminations. Pigmented water-based jet inks are commercially available, and UV-curable jet inks are in development. Pigmented inks have greater lightfastness and water-resistance.
Digital ink jet printing has the potential to revolutionize the printing industry by making short-run, color print jobs more economical. However, the next commercial stage will require significant improvements in ink jet technology; the major hurdle remaining is to improve print speed. Part of this problem is the limitation of the amount of data the printer can handle rapidly. The more complex the design, the slower the printing process. Right now they are about 10 times slower than comparable digital electrostatic printers.
Electrophotography was invented in the 1930's by Chester Carlson. By the early 1970's, the development of an electrophotographic color copier was being investigated by many companies. The technology for producing color copiers was already in place, but the market was not. It would take many more years until customer demand for color copies would create the necessary incentive to develop suitable electrostatic color copiers. By the late 1970's a few companies were using fax machines that could scan a document, reduce the images to electronic signals, send them out over the telephone wire, and, using another fax machine, retrieve the electronic signals and print the original image using heat-sensitive papers to produce a printed copy.
In 1993 Indigo and Xeikon introduced commercial digital printing machines targeted on short-run markets that were dominated by sheet-fed lithographic printers. Elimination of intermediate steps associated with negatives and plates used in offset printing provides faster turnaround and better customer service. These digital presses share some of the characteristics of traditional xerography but use very specialized inks. Unlike inks for conventional photocopiers, these inks are made with very small particle size components in the range of 1 μm. Dry toners used in xerography are typically 8-10 μm in size.
In 1995 Indigo introduced the Ominus press designed for printing flexible packaging products. The Ominus uses a digital offset color process called One Shot Color that has six colors. A key improvement has been the use of a special white Electro ink for transparent substrates. The Ominus web-fed digital printing system allows printing of various substrates using an offset cylinder that transfers the color image to the substrate. In principle, this allows perfect register regardless of the substrate being printed; paper, film, and metal can be printed by this process. This digital printing system is based on an electrophotographic process where the electrostatic image is created on the surface of a photoconductor by first charging the photo-conductor by charge corona and exposing the photoconductive surface to a light source in image fashion.
The charged electrostatic latent image is then developed using ink containing an opposite charge to that on the image. This part of the process is similar to that of electrostatic toners associated with photo-copying machines. The latent charged electrostatic image formed on the photoconductor surface is developed by means of electrophoretic transfer of the liquid toner. This electrostatic toner image is then transferred to a hot blanket, which coalesces the toner and maintains it in a tacky state until it is transferred to the substrate, which cools the ink and produces a tack-free print.
Electro inks typically comprise mineral oil and volatile organic compounds below that of conventional offset printing inks. They are designed so that the thermoplastic resin will fuse at elevated temperatures. In the actual printing process, the resin coalesced, the inks are transferred to the substrate, and there is no need to heat the ink to dry it. The ink is deposited on the substrate essentially dry, although it becomes tack-free as it cools and reaches room temperature.
For several decades a magnetic digital technology called "magnetography" has been under development. This process involves creating electrical images on a magnetic cylinder and using magnetic toners as inks to create the image. The potential advantage of this technology lies in its high press speed. Tests have shown speeds of 200 meters per minute. Although these magnetic digital printers are limited to black and white copy, developments of color magnetic inks would make this high-speed digital technology economically feasible. The key to its growth will be further development of the VHSM (very high speed magnetic) drum and the color magnetic inks.
Within the magnetic digital arena, a hybrid system called magnetolithography has been built and tested on narrow web and short-run applications developed by Nipson Printing Systems in Belfort, France. The technology appears to provide high resolution, and tests have been conducted using a silicon-based, high density, magnetographic bead. Much more work is necessary in the ink development to bring this system to a competitive position relative to ink jet or electrophotography. However, the fact that it has high speed printing potential makes it an attractive alternate for packaging applications in which today's ink jet and electrophotography technologies are lagging.
Photographic materials have been known for use as prints for preserving memories for special events such as birthdays and vacations. They also have been utilized for large display materials utilized in advertising.
Silver-halide photographic elements contain light sensitive silver halide in a hydrophilic emulsion. An image is formed in the element by exposing the silver halide to light, or to other actinic radiation, and developing the exposed silver halide to reduce it to elemental silver.
In color photographic elements, a dye image is formed as a consequence of silver halide development by one of several different processes. The most common is to allow a by-product of silver-halide development, oxidized silver-halide developing agent, to react with a compound called a coupler to form the dye image. The silver and unreacted silver halide are then removed from the photographic element, leaving a dye image.
In either case, formation of the image commonly involves liquid processing with aqueous solutions that must penetrate the surface of the element to come into contact with silver halide and coupler. Thus, gelatin and similar natural or synthetic bydrophilic6 polymers have proven to be the binders of choice for silver-halide photographic elements.
A disadvantage of gelatin and other related hydrophilic colloids, is that it is highly sensitive to relative humidity. While this is an advantage during processing, large changes in thermal characteristics and residual stresses at low relative humidity and high temperatures can cause the silver halide based label to curl and in extreme cases, lift off from the container particularly from untreated low surface energy containers such as high density polyethylene (HDPE). U.S. Pat. No. 6,265,049 describes the use of substantially water insoluble plasticizers to reduce the curl of ink jet media containing gelatin. WO 2000053406 describes the use of specific plasticizers in a gelatin containing ink jet media to reduce the curl at low humidities. Among the differences between ink jet media and conventional silver halide based,photographic media is that the latter has to undergo a wet processing step. Unless carefully chosen, the plasticizer for gelatin would wash out into the processing solution and not remain in the element to offer curl control. Further highly hydrophobic plasticizers are known to cause image deterioration by interaction with the lipophilic image dyes. It is also difficult to predict what plasticizer might reduce the curl in a highly filled system such as a photographic element. Hence there exists a need for a photographic element particularly, a silver halide based label which takes advantage of gelatin based media for processing while providing robustness towards curl as labels under a variety of humidity and temperature conditions without going into the additional expense of providing laminates to achieve the same.
In U.S. Pat. No. 5,866,282 (Bourdelais et al), a method for controlling the curl of a photographic element using a gelatin matrix for the silver halide imaging layers is discussed. By laminating high elastic modulus sheets to cellulose paper, the stiffness of the imaging base is improved, reducing the curling tendencies of the photographic element as improvement in base stiffness reduce the curl of the imaging element.
In U.S. Pat. No. 6,273,984 (Bourdelais et al), a method for manufacturing an imaging base that contains negative curl, that is curl away from the imaged surface is discussed. By thermally expanding an oriented polymer sheet just prior to lamination, the imaging base has a negative curl position as the thermally expanded polymer sheet returns to ambient temperature. The negative curl of the base offsets the positive curl tendencies of the imaging element at low humidities yielding a imaging element that is flat at low humidity.
The present invention is directed to overcoming the mechanical contraction of gelatin utilized in silver halide and ink jet imaging layers at low humidity conditions.
The invention has numerous advantages over prior practices in the art. The invention provides a printing method that is economically viable when printing short runs as the cost of printing plates or printing cylinders are avoided. The use of silver halide images for example, applied to a package ensures the highest image quality currently available compared to the common but lower quality six color rotogravure printed images. Further, because the yellow, magenta, and cyan layers contain gelatin interlayers, the silver halide images appear to have depth. Silver halide image layers have also been optimized to accurately replicate flesh tones, providing superior images of people compared to alternate prior art digital imaging technologies.
Silver halide image technology can simultaneously print text, graphics, and photographic quality images on the pressure sensitive label. Since the silver halide imaging layers of the invention are both optically and digitally compatible, text, graphics, and images can be printed using known digital printing equipment such as lasers and CRT printers. Because the silver halide system is digitally compatible, each package can contain different data thereby enabling customization of individual packages without the extra expense of printing plates or cylinders. Further, printing digital files allows the files to be transported using electronic data transfer technology such as the internet thus reducing the cycle time to apply printing to a package. Silver halide imaging layers can be digitally exposed with a laser or CRT at speeds greater than 75 meters per minute allowing competitive printing speeds compared to current ink jet or electrophotographic printing engines.
By adding flexibilizer agents to silver halide imaging layers used for consumer output, the curl of the element, particularly at low humidities can be reduced. By reducing the curl tendencies of the silver halide imaging layers, a reduction in base stiffness can be made thus reducing the material cost and content of consumer photographic print materials. Reducing the material content of the base materials allows for a reduction in shipping weight, longer rolls at the same diameter and a reduction on the use of natural resources such as cellulose fiber and polymer. For example, a 10% reduction in image curl would allow the stiffness of the imaging base to be reduced by 20 millinewtons in stiffness there by generating savings from the material reduction associated with the reduction in base stiffness. These and other advantages will be apparent from the detailed description below.
The present invention provides a novel way to control curl at low humidities and high temperatures of the final label for flexible packaging material comprising a hydrophilic imaged layer. In accordance with this invention, a flexibilizer agent is imbibed into the exposed imaging layers during processing. The flexibilizer agent has a logP of greater than −1.2 and comprises a water soluble or dispersible organic solvent to ensure an imaged element that is substantially curl free. It has been found that if the log P is less than −1.2 or greater than 5, the flexibilizer agent does not effectively imbibe into the imaged element during processing and is not therefore effective in reducing the curl of the imaged and processed element. Furthermore, in the event that the flexibilizer agent is incorporated in the imaging media prior to exposure and processing, log P less than −1.2 would cause the flexibilizer agent to wash out into the processing solution and a log P greater than 5 might cause the flexibilizer agent to have a detrimental effect on the image dyes and the physical strength of the gelatin.
The octanol-water partition coefficient is a physical property used extensively to describe a chemical's lipophilic or hydrophobic properties. It is the ratio of a chemical's concentration in the octanol-phase to its concentration in the aqueous phase of a two-phase system at equilibrium. Since measured values range from <10−4 to >10+8 (at least 12 orders of magnitude), the logarithm (log P) is commonly used to characterize its value. Log P is a valuable parameter in numerous quantitative structure-activity relationships that have been developed for the pharmaceutical, environmental, biochemical and toxicological sciences.
A gelatin based coating such as in a photographic element will have substantial residual tensile stress in the dried coating and this residual stress causes curl toward the imaging side. The magnitude of the stress and the resultant curl is a function of humidity and temperature of the environment. The curl is most profound at low humidity environment when the equilibrium amount of moisture in the gelatin coating is low. As the humidity increases, the coating absorbs moisture from the atmosphere and the moisture plasticizes the coating and reduces the tensile stress in the coating. An anhydrous gelatin coating exhibits glass transition temperature (Tg) around 175� C. The Tg decreases as the humidity increases and it reaches room temperature at 80% relative humidity. Assuming the substrate is moisture insensitive, a pure gelatin coating will experience zero stress at 80% relative humidity(RH) and it will be under tensile stress whenever the humidity falls below 80% RH.
Various flexibilizer agents may be employed in the practice of this invention to control the curl of the silver halide based label. In a particular embodiment of this invention flexibilizing agents are polyhydric alcohols and their derivatives such as. Representative flexibilizer agents for gelatin useful in the present invention are illustrated, but not limited, by the following compounds: 1,2-hexanediol, 1,6-hexanediol, 1,5-pentanediol, 2-ethyl-1-hexanol, 1,3-butanediol and 2-phenoxyethanol. The presence of these specific flexibilizer agents in the gelatin containing photographic medium have been found to reduce the curl of the medium at low humidity and high temperatures.
In a particular embodiment, the processed photographic element is further provided with an environmental protection layer in the form of a continuous protective overcoat. The environmental protection layer preferably comprises a mixture of a vinyl polymer and a urethane polymer such that, it provides environmental protection of the imaged photographic element and excellent gloss characteristics. The urethane polymer when coated in the absence of the vinyl polymer has an indentation modulus less than 0.6 GPa in a layer less than 10 micrometers in thickness The amount of the urethane polymer in the environmental protection layer can vary from 10 to 65 weight percent. In accordance with a preferred form of the present invention, a packaging label comprises in order an upper environmental protection layer, an image preferably formed by means of silver halide, a base, an adhesive, a bottom peelable back wherein said environmental protection layer comprises a vinyl polymer and a urethane polymer wherein said urethane polymer in the absence of the vinyl polymer has an indentation modulus less than 0.6 GPa in a layer less than 10 micrometers in thickness.
The flexibilizer agent can be introduced into the photographic medium in a variety of ways. In a particular embodiment it is incorporated into the gelatin layers during manufacture of the light sensitive element. It is preferred that the flexibilizer agent be present in a greater amount in the lower hydrophilic colloid layers of the photographic element. It is preferred that the recovered photographic element comprises between 0.5 and. 10 weight percent flexibilizing agent in said hydrophillic colloid layers. The flexibilizer agent may also be incorporated in the environmental protection layer. In another preferred embodiment the flexibilizer agent is imbibed into the element after exposure, during the aqueous processing step to produce the curl resistant developed photographic element. The flexibilizer agent is imbibed into the element from an aqueous solution at 1-20 weight% of the agent over a 5-90 second time period.
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. 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 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 a 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 one embodiment of 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 as 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.
Photographic elements of this invention 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 of 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. No. 4,279,945 and U.S. Pat. No. 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, 10 coating aids, plasticizers, lubricants and matting agents are described in Sections VI through X and MU 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, N.Y., 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 order to successfully transport materials of the invention, the reduction of static caused by web transport through manufacturing and image processing is desirable. Since the light sensitive imaging layers of this invention can be fogged by light from a static discharge accumulated by the web as it moves over conveyance equipment such as rollers and drive nips, the reduction of static is necessary to avoid undesirable static fog. The polymer substrate materials of this invention have a marked tendency to accumulate static charge as they contact machine components during transport. The use of an antistatic material to reduce the accumulated charge on the web materials of this invention is desirable. Antistatic materials may be coated on the web materials of this invention and may contain any known materials in the art which can be coated on photographic web materials to reduce static during the transport of photographic paper. Examples of antistatic coatings include conductive salts and colloidal silica. Desirable antistatic properties of the support materials of this invention may also be accomplished by antistatic additives which are an integral part of the polymer layer. Incorporation of additives that migrate to the surface of the polymer to improve electrical conductivity include fatty quaternary ammonium compounds, fatty amines, and phosphate esters. Other types of antistatic additives are hygroscopic compounds such as polyethylene glycols and hydrophobic slip additives that reduce the coefficient of friction of the web materials. An antistatic coating applied to the opposite side from the image layer or incorporated into the support's backside polymer layer is preferred. The backside is preferred because the majority of the web contact during conveyance in manufacturing and photoprocessing is on the backside. The backside is the side not carrying the emulsion containing image forming layers. The preferred surface resistivity of the antistat coat at 50% RH is less than 1013 ohm/square. A surface resistivity of the antistat coat at 50% RH is less than 1013 ohm/square and has been shown to sufficiently reduce static fog in manufacturing and during photoprocessing of the image layers.
Conductive layers can be incorporated into multilayer imaging elements in any of various configurations depending upon the requirements of the specific imaging 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 imaging 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 imaging 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 imaging 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 imaging 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.
Conductive layers underlying a transparent magnetic recording layer typically exhibit an internal resistivity of less than 1�1010 ohms/square, preferably less than 1�109 ohms/square, and more preferably, less than 1�108 ohms/square.
The terms as used herein, "top", "upper", "emulsion side", and "face" mean the side or toward the side of a packaging material bearing the imaging layers. The term environmental protection layer means the layer applied over the imaging layers after image formation. The terms "face stock", "substrate" and "base" mean the material to which the hydrophilic imaging layers such as silver halide layers are applied. The terms "bottom", "lower side", and "back" mean the side or toward the side of the label or packaging material opposite from the side bearing the images formed in a gelatin media.
In order to produce a pressure sensitive photographic label, the liner material that carries the pressure sensitive adhesive, face stock and imaged layers, the liner material must allow for efficient transport in manufacturing, image printing, image development, label converting and label application equipment. A label comprising a silver halide imaging layer, a base and a strippable liner connected by an adhesive to said base, wherein said base has a stiffness of between 15 and 60 mN and an L* is greater than 92.0, and wherein said liner has a stiffness of between 40 and 120 mN is preferred. The photographic label packaging material is preferred with the white, stiff liner as it allows for efficient transport through photographic printing and processing equipment and improves printing speed compared to typical liner materials that are brown or clear and have little contribution to secondary exposure.
A peelable liner or back is preferred as the pressure sensitive adhesive required for adhesion of the label to the package, can not be transported through labeling equipment without the liner. The liner provides strength for conveyance and protects the pressure sensitive adhesive prior to application to the package. A preferred liner material is cellulose paper. A cellulose paper liner is flexible, strong and low in cost compared to polymer substrates. Further, a cellulose paper substrate allows for a textured label surface that can be desirable in some packaging applications. The paper may preferably be provided with coatings that will provide waterproofing to the paper as the photographic element of the invention must be processed in aqueous chemistry to develop the image. Examples of a suitable water proof coatings applied to the paper are acrylic polymer, melt extruded polyethylene and oriented polyolefin sheets laminated to the paper. Paper is also preferred as paper can contain moisture and salt which provide antistatic properties that prevent static sensitization of the silver halide image layers.
Further, paper containing sizing agents, known in the photographic paper art and disclosed in U.S. Pat. No. 6,093,521, provide resistance to edge penetration of the silver halide image processing chemistry. An edge penetration of less than 8 micrometers is preferred as processing chemistry penetrated into the paper greater than 12 micrometers has been shown to swell causing die cutting problems when face stock matrix is die cut and stripped from the liner. Also, penetration of processing chemistry greater than 12 micrometers increases the chemistry usage in processing resulting in higher processing costs.
Another preferred liner material or peelable back is an oriented sheet of polymer. The liner preferably is an oriented polymer because of the strength and toughness developed in the orientation process. Preferred polymers for the liner substrate include polyolefins, polyester and nylon. Preferred polyolefin polymers include polypropylene, polyethylene, polymethylpentene, polystyrene, polybutylene, and mixtures thereof Polyolefin copolymers, including copolymers of propylene and ethylene such as hexene, butene, and octene are also useful. Polyester is most preferred, as it is has desirable strength and toughness properties required for efficient transport of silver halide pressure sensitive label liner in high speed labeling equipment.
In another preferred embodiment, the liner consists of a paper core to which sheets of oriented polymer are laminated. The laminated paper liner is preferred because the oriented sheets of polymer provide tensile strength which allows the thickness of the liner to be reduced compared to coated paper and the oriented polymer sheet provides resistance to curl during manufacturing and drying in the silver halide process.
The tensile strength of the liner or the tensile stress at which a substrate breaks apart is an important conveyance and forming parameter. Tensile strength is measured by ASTM D882 procedure. A tensile strength greater than 120 MPa is preferred as liners less than 110 MPa begin to fracture in automated packaging equipment during conveyance, forming and application to the package.
The coefficient of friction or COF of the liner bearing the silver halide imaging layer is an important characteristic as the COF is related to conveyance and forming efficiency in automated labeling equipment. COF is the ratio of the weight of an item moving on a surface to the force that maintains contact between the surface and the item. The mathematical expression for COF is as follows:
The COF of the liner is measured using ASTM D-1894 utilizing a stainless steel sled to measure both the static and dynamic COF of the liner. The preferred COF for the liner of the invention is between 0.2 and 0.6. As an example, a 0.2 COF is necessary for coating on a label used in a pick-and-place application. The operation using a mechanical device to pick a label and move it to another point requires a low COF so the label will easily slide over the surface of the label below it. At the other extreme, large sheets such as book covers require a 0.6 COF to prevent them from slipping and sliding when they are piled on top of each other in storage. Occasionally, a particular material may require a high COF on one side and a low COF on the other side. Normally, the base material itself, such as a plastic film, foil, or paper substrate, would provide the necessary COF for one side. Application of an appropriate coating would modify the image side to give the higher or lower value. Conceivably, two different coatings could be used with one on either side. COF can be static or kinetic. The coefficient of static friction is the value at the time movement between the two surfaces is ready to start but no actual movement has occurred. The coefficient of kinetic friction refers to the case when the two surfaces are actually sliding against each other at a constant rate of speed. COF is usually measured by using a sled placed on the surface. The force necessary at the onset of sliding provides a measurement of static COF. Pulling the sled at a constant speed over a given length provides a measure of kinetic frictional force.
The preferred thickness of the liner utilized with the invention is between 75 and 225 micrometers. Thickness of the liner is important in that the strength of the liner, expressed in terms of tensile strength or mechanical modulus, must be balanced with the thickness of the liner to achieve a cost efficient design. For example, thick liners that are high in strength are not cost efficient because thick liners will result in short roll lengths compared to thin liners at a given roll diameter. A liner thickness less that 60 micrometer has been shown to cause transport failure in the edge guided silver halide printers. A liner thickness greater than 250 micrometers yields a design that is not cost effective and is difficult to transport in existing silver halide printers.
The liner utilized with the invention preferably has an optical transmission of less than 20%. During the printing of the silver halide labels, exposure light energy is required to reflect from the face stock/liner combination to yield a secondary exposure. This secondary exposure is critical to maintaining high level of printing productivity. It has been shown that liners with an optical transmission of greater than 25% significantly reduces the printing speed of the silver halide label. Further, clear face stock material to provide the "no label look" need an opaque liner to not only maintain printing speed, but to prevent unwanted reflection from printing platens in current silver halide printers.
Since the light sensitive silver halide layers with expanded color gamut can suffer from unwanted exposure from static discharge during manufacturing, printing and processing, the liner preferably has a resistivity of less than 1011 ohms/square. A wide variety of electrically-conductive materials can be incorporated into antistatic layers to produce a wide range of conductivities. These can be divided into two broad groups: (i) ionic conductors and (ii) electronic conductors. In ionic conductors charge is transferred by the bulk diffusion of charged species through an electrolyte. Here the resistivity of the antistatic layer is dependent on temperature and humidity. Antistatic layers containing simple inorganic salts, alkali metal salts of surfactants, ionic conductive polymers, polymeric electrolytes containing alkali metal salts, and colloidal metal oxide sols (stabilized by metal salts), described previously in patent literature, fall in this category. However, many of the inorganic salts, polymeric electrolytes, and low molecular weight surfactants used are water-soluble and are leached out of the antistatic layers during processing, resulting in a loss of antistatic function. The conductivity of antistatic layers employing an electronic conductor depends on electronic mobility rather than ionic mobility and is independent of humidity. Antistatic layers which contain conjugated polymers, semiconductive metal halide salts, semiconductive metal oxide particles, etc. have been described previously. However, these antistatic layers typically contain a high volume percentage of electronically conducting materials which are often expensive and impart unfavorable physical characteristics, such as color, increased brittleness, and poor adhesion to the antistatic layer.
In a preferred embodiment of this invention the label has an antistat material incorporated into the liner or coated on the liner. It is desirable to have an antistat that has an electrical surface resistivity of at least 1011 log ohms/square. In the most preferred embodiment, the antistat material comprises at least one material selected from the group consisting of tin oxide and vanadium pentoxide.
In another preferred embodiment of the invention antistatic material are incorporated into the pressure sensitive adhesive layers. The antistatic material incorporated into the pressure sensitive adhesive layer provides static protection to the silver halide layers and reduces the static on the photographic label which has been shown to aid labeling of containers in high speed labeling equipment. As a stand-alone or supplement to the liner comprising an antistatic layer, the pressure sensitive adhesive may also further comprise an antistatic agent selected from the group consisting of conductive metal oxides, carbon particles, and synthetic smectite clay, or multi-layered with an inherently conductive polymer. In one of the preferred embodiments, the antistat material is metal oxides. Metal oxides are preferred because they are readily dispersed in the thermoplastic adhesive and can be applied to the polymer sheet by any means known in the art. Conductive metal oxides that may be useful in this invention are selected from the group consisting of conductive particles including doped-metal oxides, metal oxides containing oxygen deficiencies, metal antimonates, conductive nitrides, carbides, or borides, for example, TiO2, SnO2, Al.2O3, ZrO3, In2O3, MgO, ZnSb2O6, InSbO4, TiB2, ZrB2, NbB2, TaB2, CrB2, MoB, WB, LaB6, ZrN, TiN, TiC, and WC. The most preferred materials are tin oxide and vanadium pentoxide because they provide excellent conductivity and are transparent.
The base material, or the flexible substrate utilized in this invention on to which the light sensitive silver halide imaging layers are applied, must not interfere with the silver halide imaging layers. Further, the base material of this invention needs to optimize the performance of the silver halide imaging system. Suitable flexible substrates must also perform efficiently in a automated packaging equipment for the application of photographic labels to various containers. A preferred flexible substrate is cellulose paper. A cellulose paper substrate is flexible, strong and low in cost compared to polymer substrates. Further, a cellulose paper substrate allows for a textured photographic label surface that can be desirable in some packaging applications. The paper preferably is provided with coatings that will provide waterproofing to the paper as the photographic element of the invention must be processed in aqueous chemistry to develop the silver halide image. An example of a suitable waterproof coating is acrylic or polyethylene polymer.
Polymer substrates are another preferred base material because they are tear resistant, have excellent conformability, good chemical resistance and are high in strength. Preferred polymer substrates include polyester, oriented polyolefin such as polyethylene and polypropylene, cast polyolefins such as polypropylene and polyethylene, polystyrene, acetate and vinyl. Polymers are preferred as they are strong and flexible and provide an excellent surface for the coating of silver halide imaging layers.
Biaxially oriented polyolefin sheets are preferred as they are low in cost, have excellent optical properties that optimize the silver halide system and can be applied to packages in high speed labeling equipment. Microvoided composite biaxially oriented sheets are most preferred because the voided layer provides opacity and lightness without the need for TiO2. Also, the voided layers of the microvoided biaxially oriented sheets have been shown to significantly reduce pressure sensitivity of the silver halide imaging layers. Microvoided biaxially oriented sheets are conveniently manufactured by coextrusion of the core and surface layers, followed by biaxial orientation, whereby voids are formed around void-initiating material contained in the core layer. Such composite sheets are disclosed in U.S. Pat. Nos. 4,377,616; 4,758,462; 4,632,869 and 5,866,282. The biaxially oriented polyolefin sheets also may be laminated to one or both sides of a paper sheet to form a photographic label with greater stiffness if that is needed.
The flexible polymer base substrate may contain more than one layer. The skin layers of the flexible substrate can be made of the same polymeric materials as listed above for the core matrix. The composite sheet can be made with skin(s) of the same polymeric material as the core matrix, or it can be made with skin(s) of different polymeric composition than the core matrix. For compatibility, an auxiliary layer can be used to promote adhesion of the skin layer to the core.
Voided biaxially oriented polyolefin sheets are a preferred flexible base substrate for the coating of light sensitive silver halide imaging layers. Voided films are preferred as they provide opacity, whiteness and image sharpness to the image. "Void" is used herein to mean devoid of added solid and liquid matter, although it is likely the "voids" contain gas. The void-initiating particles which remain in the finished packaging sheet core should be from 0.1 to 10 μm in diameter and preferably round in shape to produce voids of the desired shape and size. The size of the void is also dependent on the degree of orientation in the machine and transverse directions. Ideally, the void would assume a shape which is defined by two opposed and edge contacting concave disks. In other words, the voids tend to have a lens-like or biconvex shape. The voids are oriented so that the two major dimensions are aligned with the machine and transverse directions of the sheet. The Z-direction axis is a minor dimension and is roughly the size of the cross diameter of the voiding particle. The voids generally tend to be closed cells, and thus there is virtually no path open from one side of the voided-core to the other side through which gas or liquid can traverse.
The photographic element of this invention generally has a glossy surface, that is, a surface that is sufficiently smooth to provide excellent reflection properties. An opalescent surface may be preferred because it provides a unique photographic appearance to a photographic label that is perceptually preferred by consumers. The opalescent surface is achieved when the microvoids in the vertical direction are between 1 and 3 μm. By the vertical direction, it is meant the direction that is perpendicular to the plane of the imaging member. The thickness of the microvoids preferably is between 0.7 and 1.5 μm for best physical performance and opalescent properties. The preferred number of microvoids in the vertical direction is between 8 and 30. Less than 6 microvoids in the vertical direction do not create the desired opalescent surface. Greater than 35 microvoids in the vertical direction do not significantly improve the optical appearance of the opalescent surface.
The void-initiating material for the flexible base substrate may be selected from a variety of materials and should be present in an amount of about 5 to 50% by weight based on the weight of the core matrix polymer. Preferably, the void-initiating material comprises a polymeric material. When a polymeric material is used, it may be a polymer that can be melt-mixed with the polymer from which the core matrix is made and be able to form dispersed spherical particles as the suspension is cooled down. Examples of this would include nylon dispersed in polypropylene, polybutylene terephthalate in polypropylene, or polypropylene dispersed in polyethylene terephthalate. If the polymer is preshaped and blended into the matrix polymer, the important characteristic is the size and shape of the particles. Spheres are preferred and they can be hollow or solid. These spheres may be made from cross-linked polymers which are members selected from the group consisting of an alkenyl aromatic compound having the general formula Ar—C(R)═CH2, wherein Ar represents an aromatic hydrocarbon radical, or an aromatic halohydrocarbon radical of the benzene series and R is hydrogen or the methyl radical, acrylate-type monomers include monomers of the formula CH2═C(R′)—C(O)(OR) wherein R is selected from the group consisting of hydrogen and an alkyl radical containing from about 1 to 12 carbon atoms and R′ is selected from the group consisting of hydrogen and methyl; copolymers of vinyl chloride and vinylidene chloride, acrylonitrile and vinyl chloride, vinyl bromide, vinyl esters having formula CH2═CH(O)COR, wherein R is an alkyl radical containing from 2 to 18 carbon atoms; acrylic acid, methacrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, oleic acid, vinylbenzoic acid; the synthetic polyester resins which are prepared by reacting terephthalic acid and dialkyl terephthalics or ester-forming derivatives thereof, with a glycol of the series HO(CH2)nOH wherein n is a whole number within the range of 2-10 and having reactive olefinic linkages within the polymer molecule, the above-described polyesters which include copolymerized therein up to 20 percent by weight of a second acid or ester thereof having reactive olefinic unsaturation and mixtures thereof, and a cross-linking agent selected from the group consisting of divinylbenzene, diethylene glycol dimethacrylate, diallyl fumarate, diallyl phthalate; and mixtures thereof.
Examples of typical monomers for making the cross-linked polymer void initiating particles include styrene, butyl acrylate, acrylamide, acrylonitrile, methyl methacrylate, ethylene glycol dimethacrylate, vinyl pyridine, vinyl acetate, methyl acrylate, vinylbenzyl chloride, vinylidene chloride, acrylic acid, divinylbenzene, acrylamidomethyl-propane sulfonic acid, vinyl toluene, etc. Preferably, the cross-linked polymer is polystyrene or poly(methyl methacrylate). Most preferably, it is polystyrene, and the cross-linking agent is divinylbenzene.
Processes well known in the art yield nonuniformly sized void initiating particles, characterized by broad particle size distributions. The resulting beads can be classified by screening the beads spanning the range of the original distribution of sizes. Other processes such as suspension polymerization, limited coalescence, directly yield very uniformly sized particles.
The void-initiating materials may be coated with agents to facilitate voiding. Suitable agents or lubricants include colloidal silica, colloidal alumina, and metal oxides such as tin oxide and aluminum oxide. The preferred agents are colloidal silica and alumina, most preferably, silica. The cross-linked polymer having a coating of an agent may be prepared by procedures well known in the art. For example, conventional suspension polymerization processes wherein the agent is added to the suspension is preferred. As the agent, colloidal silica is preferred.
The void-initiating particles can also be inorganic spheres, including solid or hollow glass spheres, metal or ceramic beads or inorganic particles such as clay, talc, barium sulfate, or calcium carbonate. The important thing is that the material does not chemically react with the core matrix polymer to cause one or more of the following problems: (a) alteration of the crystallization kinetics of the matrix polymer, making it difficult to orient, (b) destruction of the core matrix polymer, (c) destruction of the void-initiating particles, (d) adhesion of the void-initiating particles to the matrix polymer, or (e) generation of undesirable reaction products, such as toxic or high color moieties. The void-initiating material should not be photographically active or degrade the performance of the photographic element in which the biaxially oriented polyolefin sheet is utilized.
The total thickness of the topmost skin layer of the polymeric base substrate may be between 0.20 μm and 1.5 μm, preferably between 0.5 and 1.0 μm. Below 0.5 μm any inherent nonplanarity in the coextruded skin layer may result in unacceptable color variation. At skin thickness greater than 1.0 μm, there is a reduction in the photographic optical properties such as image resolution. At thickness greater than 1.0 μm, there is also a greater material volume to filter for contamination such as clumps or poor color pigment dispersion.
Addenda may be added to the top most skin layer of the flexible base substrate to change the color of the imaging element. For labeling use, a white substrate with a slight bluish tinge is preferred. The addition of the slight bluish tinge may be accomplished by any process which is known in the art including the machine blending of color concentrate prior to extrusion and the melt extrusion of blue colorants that have been preblended at the desired blend ratio. Colored pigments that can resist extrusion temperatures greater than 320� C. are preferred, as temperatures greater than 320� C. are necessary for coextrusion of the skin layer. Blue colorants used in this invention may be any colorant that does not have an adverse impact on the imaging element. Preferred blue colorants include Phthalocyanine blue pigments, Cromophtal blue pigments, Irgazin blue pigments, and Irgalite organic blue pigments. Optical brightener may also be added to the skin layer to absorb UV energy and emit light largely in the blue region. TiO2 may also be added to the skin layer. While the addition of TiO2 in the thin skin layer of this invention does not significantly contribute to the optical performance of the sheet, it can cause numerous manufacturing problems such as extrusion die lines and spots. The skin layer substantially free of TiO2 is preferred. TiO2 added to a layer between 0.20 and 1.5 μm does not substantially improve the optical properties of the support, will add cost to the design, and will cause objectionable pigments lines in the extrusion process.
Addenda may be-added to the core matrix and/or to one or more skin layers to improve the optical properties of the flexible substrate. Titanium dioxide is preferred and is used in this invention to improve image sharpness or MTF, opacity, and whiteness. The TiO2 used may be either anatase or rutile type. Further, both anatase and rutile TiO2 may be blended to improve both whiteness and sharpness. Examples of TiO2 that are acceptable for a photographic system are DuPont Chemical Co. R101 rutile TiO2 and DuPont Chemical Co. R104 rutile TiO2. Other pigments known in the art to improve photographic optical responses may also be used in this invention. Examples of other pigments known in the art to improve whiteness are talc, kaolin, CaCO3, BaSO4, ZnO, TiO2, ZnS, and MgCO3. The preferred TiO2 type is anatase, as anatase TiO2 has been found to optimize image whiteness and sharpness with a voided layer.
The voids provide added opacity to the flexible substrate. This voided layer can also be used in conjunction with a layer that contains at least one pigment from the group consisting of TiO2, CaCO3, clay, BASO4, ZnS, MgCO3, talc, kaolin, or other materials that provide a highly reflective white layer in said film of more than one layer. The combination of a pigmented layer with a voided layer provides advantages in the optical performance of the final image.
The flexible biaxially base substrate of this invention which has a microvoided core is preferred. The microvoided core adds opacity and whiteness to the imaging support, further improving imaging quality. Combining the image quality advantages of a microvoided core with a material, which absorbs ultraviolet energy and emits light in the visible spectrum, allows for the unique optimization of image quality, as the image support can have a tint when exposed to ultraviolet energy yet retain excellent whiteness when the image is viewed using lighting that does not contain significant amounts of ultraviolet energy such as indoor lighting.
It has been found that the microvoids located in the voided layer of the flexible biaxially oriented substrate provide a reduction in undesirable pressure fog. Mechanical pressure, of the order of hundreds of kilograms per square centimeter, causes an undesirable, reversible decrease in sensitivity by a mechanism at the time of writing that is not fully understood. The net result of mechanical pressure is an unwanted increase in density, mainly yellow density. The voided layer in the biaxially oriented flexible substrate absorbs mechanical pressure by compression of the voided layer, common in the converting and photographic processing steps, and reduces the amount of yellow density change. Pressure sensitivity is measured by applying a 206 MPa load to the coated light sensitive silver halide emulsion, developing the yellow layer, and measuring the density difference with an X-Rite model 310 (or comparable) photographic transmission densitometer between the control sample which was unloaded and the loaded sample. The preferred change in yellow layer density is less than 0.02 at a pressure of 206 MPa. A 0.04 change in yellow density is perceptually significant and, thus, undesirable.
The coextrusion, quenching, orienting, and heat setting of the flexible base substrate may be effected by any process which is known in the art for producing oriented sheet, such as by a flat sheet process or a bubble or tubular process. The flat sheet process involves extruding the blend through a slit die and rapidly quenching the extruded web upon a chilled casting drum so that the core matrix polymer component of the sheet and the skin components(s) are quenched below their glass solidification temperature. The quenched sheet is then biaxially oriented by stretching in mutually perpendicular directions at a temperature above the glass transition temperature and below the melting temperature of the matrix polymers. The sheet may be stretched in one direction and then in a second direction or may be simultaneously stretched in both directions. After the sheet has been stretched, it is heat set by heating to a temperature sufficient to crystallize or anneal the polymers, while restraining to some degree the sheet against retraction in both directions of stretching.
By having at least one nonvoided skin on the microvoided core, the tensile strength of the flexible base substrate is increased and makes the sheet more manufacturable. The higher tensile strength also allows the sheets to be made at wider widths and higher draw ratios than when sheets are made with all layers voided. Coextruding the layers further simplifies the manufacturing process.
In order to provide a digital printing technology that can be applied to a package that is high in quality, can handle text, graphic and images, is economical for short run printing jobs and accurately reproduce flesh tones, silver halide imaging is preferred. The silver halide technology can be either black and white or color. The silver halide imaging layers are preferably exposed and developed prior to application to a package. The flexible substrate of the invention contains the necessary tensile strength properties and coefficient of friction properties to allow for efficient transport and application of the images in high speed labeling equipment. The substrate of the invention is formed by applying light sensitive silver halide imaging layers of a flexible label stock that contains a pressure sensitive adhesive. The imaging layers, face stock and pressure sensitive adhesive are supported and transported through labeling equipment using a tough liner material.
The following examples are used to illustrate the present invention. However, it should be understood that the invention is not limited to these illustrative examples.
The examples for the curl tests were conducted on paper that was previously coated with light sensitive emulsions in a color paper formulation described in Tables 1 and 2 below. The gelatin containing layers were hardened with bis(vinylsulfonyl methyl) ether at 1.95% of the total gelatin weight.
Laydown (g/m2)
0.557 Gelatin
0.204 Silica
0.17 Polydimethylsiloxane
0.446 Gelatin
0.16 Red light sensitive AgX
1.170 Gelatin
0.630 Gelatin
0.067 Green-light sensitive AgX
1.087 Gelatin
0.650 Gelatin
0.186 Blue-light sensitive AgX
1.133 Gelatin
Photographic Paper Support
sublayer 1: resin coat (Titanox and optic brightener in polyethylene)
sublayer 2: paper
sublayer 3: resin coat-(polyethylene)
Butanamide 2-[2,4-bis(1,1-dimethylpropyl)phenoxy]-N-
1,4-Cyclohexylenedimethylene bis(2-ethylhexaneoate)
2-(2-Butoxyethoxy)ethyl acetate
benzenesulfonic acid 2,5-dihydroxy-4-(1-methylheptadecyl)-
mono-potassium salt
The color paper samples were exposed to white light and processed using the Kodak RA4 Process according to the sequence given in Table 3.
Time (sec)
Flexibilizer agent treatment
Table 4 lists the various flexibilizer agents that were used to provide curl resistance to the photographic element. These agents were prepared as 10 percent by weight aqueous solutions and introduced into the processing sequence prior to the rinse solution, in the processing sequence described above.
Chemical Composition
Log P
None (control)
FA1 (invention)
FA2 (invention)
FA3 (invention)
FA4 (invention)
FA5 (invention)
FA6 (invention)
FA7 (invention)
Ethylene glycol
sodium salt
Curl Test
After RA-4 processing, the color paper with each of the imbibed flexibilizing agents and the control were dried at 55� C. for 60 minutes. The processed papers were cut into 1″�1″ squares and placed on a flat stainless steel plate with the imaged side up. The plate was kept in a 120� F. oven at 10%RH for 24 hours. The extent of curl was determined by measuring the distance between the plate and the corner of each square most lifted from the plate for each of the samples. Positive curl is curl that is towards the imaged side and negative curl is curl that is away from the image. Comparing the curl of the control (example 1) which exhibited positive curl, to the samples with the imbibed flexibilizer agents, in all cases those agents with log P greater than −1.2 (examples 2-8) caused the processed color paper to curl 50-100% less than the check away from the imaged side. Examples 9-11 on the other hand showed no improvement over the control because of their greater water solubility and inefficient partitioning into the gelatin based imaging element.
These experiments were done using a silver halide based label using the formulation and architecture described below.
A silver halide pressure sensitive packaging label was created by applying a light sensitive silver halide color imaging layers to a pressure sensitive label stock. The label stock consisted of a flexible white biaxially oriented polypropylene face stock coated with a pressure sensitive adhesive that was laminated to a high strength polyester liner. The light sensitive silver halide imaging layers were a yellow, magenta, and cyan coupler system capable of accurate reproduction of flesh tone. Biaxially oriented polyolefin face stock:
A composite sheet polyolefin sheet (31 μm thick) (d=0.68 g/cc) consisting of a microvoided and oriented polypropylene core (approximately 60% of the total sheet thickness), with a homopolymer non-microvoided oriented polypropylene layer on each side of the voided layer, the void initiating material used was poly(butylene terephthalate). The polyolefin sheet had a skin layer consisting of polyethylene and a blue pigment. The polypropylene layer adjacent the voided layer contained 4% rutile TiO2 and optical brightener. The silver halide imaging layers were applied to the blue tinted polyethylene skin layer. Pressure sensitive adhesive:
Permanent water based acrylic adhesive 12 μm thick Polyester liner:
A polyethylene terephthalate liner 37 μm thick that was transparent. The polyethylene terephthalate base had a stiffiess of 15 millinewtons in the machine direction and 20 millinewtons in the cross direction. Structure of the photographic packaging label material prior to adding the image layer of the example is as follows:
Voided polypropylene base
Acrylic pressure sensitive adhesive
Polyester liner
Silver chloride emulsions were chemically and spectrally sensitized as described below. A biocide comprising a mixture of N-methyl-isothiazolone and N-methyl-5-chloro-isthiazolone was added after sensitization.
Blue Sensitive Emulsion (Blue EM-1). A high chloride silver halide emulsion is precipitated by adding approximately equimolar silver nitrate and sodium chloride solutions into a well-stirred reactor containing glutaryldiaminophenyldisulfide, gelatin peptizer, and thioether ripener. Cesium pentachloronitrosylosmate(II) dopant is added during the silver halide grain formation for most of the precipitation, followed by the addition of potassium hexacyanoruthenate(II), potassium (5-methyl-thiazole)-pentachloroiridate, a small amount of KI solution, and shelling without any dopant. The resultant emulsion contains cubic-shaped grains having edge length of 0.6 μm. The emulsion is optimally sensitized by the addition of a colloidal suspension of aurous sulfide and heat ramped to 60� C. , during which time blue sensitizing dye BSD-4, potassium hexchloroiridate, Lippmann bromide, and 1-(3-acetamidophenyl)-5-mercaptotetrazole were added.
Green Sensitive Emulsion (Green EM-1): A high chloride silver halide emulsion is precipitated by adding approximately equimolar silver nitrate and sodium chloride solutions into a well-stirred reactor containing gelatin peptizer and thioether ripener. Cesium pentachloronitrosylosmate(II) dopant is added during the silver halide grain formation for most of the precipitation, followed by the addition of potassium (5-methylthiazole)-pentachloroiridate. The resultant emulsion contains cubic-shaped grains of 0.3 μm in edge length size. The emulsion is optimally sensitized by the addition of glutaryldiaminophenyldisulfide, a colloidal suspension of aurous sulfide and heat ramped to 55� C., during which time potassium hexchloroiridate doped Lippmann bromide, a liquid crystalline suspension of green sensitizing dye GSD-1, and 1-(3-acetamidophenyl)-5-mercaptotetrazole were added.
Red Sensitive Emulsion (Red EM-1): A high chloride silver halide emulsion is precipitated by adding approximately equimolar silver nitrate and sodium chloride solutions into a well-stirred reactor containing gelatin peptizer and thioether ripener. During the silver halide grain formation, potassium hexacyanoruthenate(II) and potassium (5-methylthiazole)-pentachloroiridate are added. The resultant emulsion contains cubic shaped grains of 0.4 μm in edge length size. The emulsion is optimally sensitized by the addition of glutaryldiaminophenyldisulfide, sodium thiosulfate, tripotassium bis {2-[3-(2-sulfobenzamido)phenyl]-mercaptotetrazole} gold(I) and heat ramped to 64� C., during which time 1-(3-acetamidophenyl)-5-mercaptotetrazole, potassium hexchloroiridate, and potassium bromide are added. The emulsion is then cooled to 40� C., pH adjusted to 6.0, and red sensitizing dye RSD-1 is added.
Coupler dispersions were emulsified by methods well known to the art, and the following layers were coated on the following support: The following flesh tone optimized light sensitive silver halide imaging layers were utilized to prepare photographic label utilizing the invention label base material. The following imaging layers were coated utilizing curtain coating. The gelatin containing layers were hardened with bis(vinylsulfonyl methyl) ether at 1.95% of the total gelatin weight.
Laydown (g/m2)
Layer 1
Blue Sensitive Layer
Blue sensitive silver (Blue EM-1)
Tributyl Citrate
Sodium Phenylmercaptotetrazole
Piperidino hexose reductone
Potassium chloride
Layer 2
Catechol disulfonate
Layer 3
Green Sensitive Layer
Green sensitive silver (Green EM-1)
Oleyl Alcohol
Potassium chloride
Sodium Phenylmercaptotetrazole
Layer 4
M/C Interlayer
Acrylamide/t-Butylacrylamide sulfonate
3,5-Dinitrobenzoic acid
Citric acid
Catechol disulfonate
Layer 5
Red Sensitive Layer
Red Sensitive silver (Red EM-1)
Dibutyl sebacate
Potassium p-toluenethiosulfonate
Sodium Phenylmercaptotetrazole
Layer 6
UV Overcoat
Layer 7
Ludox AM ™ (colloidal silica)
Polydimethylsiloxane (DC200 ™)
Tergitol 15-S-5 ™ (surfactant)
Aerosol OT ™ (surfactant)
The light sensitive silver halide emulsion coated on the label support of this example were exposed to white light and processed using the Kodak RA4 Process according to the sequence given in Table 3. Example 12 used no flexibilizer agent and was treated as the control. Example 13 used FA2 (1,3-butanediol) as the flexibilizing agent.
Label Test
The processed silver halide packing label material described in examples 12 and 13 were cut into 2″�3″ labels and hand applied to round untreated HDPE bottles to simulate application of the label to a package. The bottles were placed in a controlled humidity oven at 120� F. and 10%RH for 24 hours and the label lift-off from the bottle determined by measuring the measuring the distance between the bottle and the corner of each label most lifted from the bottle for each of the samples. Examples 13 showed a 75% reduction in curl compared to the control, example 12 that used no flexibilizer agent.
While this invention was directed toward base materials that are typical of product labeling applications, mainly base materials with a stiffness less than 20 millinewtons, the reduction of curl can also be applied to consumer photographic print material. By applying the flexibilizer agents to consumer print materials, the curl of images can be reduced at low humidity, improving the quality of the image and improving the easy of viewing by consumers.
Diundecyl Phthalate S-3
Tris(2-ethylhexyl)phosphate S-6
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.
Cited Patent | Filing date | Publication date | Applicant | Title |
US2960404 * | Jun 4, 1956 | Nov 15, 1960 | Eastman Kodak Co | Gelatin coating compositions |
US3042524 * | Feb 12, 1958 | Jul 3, 1962 | Gen Aniline & Film Corp | Plasticized gelatin and related proteinaceous colloids |
US5128236 * | Jun 27, 1990 | Jul 7, 1992 | E. I. Du Pont De Nemours And Company | Drying with improved physical performance of photographic films |
US5370982 * | Oct 19, 1993 | Dec 6, 1994 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
US5716764 * | Apr 10, 1996 | Feb 10, 1998 | Eastman Kodak Company | Photographic silver halide element having improved storage stability |
US5866282 | May 23, 1997 | Feb 2, 1999 | Eastman Kodak Company | Composite photographic material with laminated biaxially oriented polyolefin sheets |
US6045965 * | Nov 20, 1998 | Apr 4, 2000 | Eastman Kodak Company | Photographic member with peelable and repositioning adhesive layer |
US6130024 * | Nov 20, 1998 | Oct 10, 2000 | Eastman Kodak Company | Strippable repositionable back sheet for photographic element |
US6265049 | May 25, 1999 | Jul 24, 2001 | Hewlett-Packard Company | Inkjet printing media containing substantially water-insoluble plasticizer |
US6273984 | Nov 20, 1998 | Aug 14, 2001 | Eastman Kodak Company | Lamination with curl control |
US6277547 * | Sep 30, 1999 | Aug 21, 2001 | Eastman Kodak Company | Flexible silver halide packaging material |
US6436604 * | Jan 30, 2001 | Aug 20, 2002 | Eastman Kodak Company | Photographic label suitable for packaging |
WO2000053406A1 | Feb 29, 2000 | Sep 14, 2000 | Rexam Graphics Inc. | High gloss ink jet receiving medium |
Citing Patent | Filing date | Publication date | Applicant | Title |
US7014910 | Apr 15, 2004 | Mar 21, 2006 | Eastman Kodak Company | Sensual label |
US20040197524 * | Apr 15, 2004 | Oct 7, 2004 | Rochford William T. | Sensual label |
US20080087376 * | Sep 13, 2007 | Apr 17, 2008 | 3M Innovative Properties Company | Method of making a photographic print with an adhesive composite |
US20080087379 * | Sep 13, 2007 | Apr 17, 2008 | 3M Innovative Properties Company | Repositionable adhesive-backed photographs and photo media and methods of making |
US20090075007 * | Sep 13, 2007 | Mar 19, 2009 | 3M Innovative Properties Company | Adhesive composite |
US20090075070 * | Sep 13, 2007 | Mar 19, 2009 | 3M Innovative Properties Company | Photographic print with an adhesive composite |
U.S. Classification | 430/259, 430/432, 430/539, 430/493, 430/631, 430/627, 430/523, 430/930, 430/638 |
International Classification | G03C1/76, G03C1/31, G03C1/06, G03C1/805, G03C1/81 |
Cooperative Classification | Y10S430/131, G03C1/31, G03C1/81, G03C1/805, G03C1/7614 |
European Classification | G03C1/805, G03C1/81, G03C1/76D, G03C1/31 |
Date | Code | Event | Description |
Dec 21, 2001 | AS | Assignment | Owner name: EASTMAN KODAK COMPANY, NEW YORK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NAIR, MRIDULA;BOURDELAIS, ROBERT P.;GREENER, JEHUDA;REEL/FRAME:012442/0265;SIGNING DATES FROM 20011211 TO 20011213 |
Mar 20, 2007 | FPAY | Fee payment | Year of fee payment: 4 |
Jun 20, 2011 | REMI | Maintenance fee reminder mailed | |
Nov 11, 2011 | LAPS | Lapse for failure to pay maintenance fees | |
Jan 3, 2012 | FP | Expired due to failure to pay maintenance fee | Effective date: 20111111 |


text:
Performance for your privates! Discreet boxers for wearing underneath a pair of shorts. Designed to perfection with a nice attention to detail. Pro Cool functional underwear is designed specifically to keep you cool while exercising in warm conditions. Using HEXA continuous filament fabric it pulls perspiration vapour off the body to keep it cool. Key Features: Ergonomic fit for total freedom of movements. Antimicrobial EI Light Men Chamois. Pro Cool Mesh panels in sides. Slim and lightweight fit. Super cooling effect. Excellent moisture transportation. Odour resistant fabric. Non padded boxer. Due to hygiene reasons these cant be returned.
Check stock and price

subset: commoncrawl


text:
The Black Nativity, the season's newest holiday film, boldly displays the true meaning of faith and forgiveness. The musically delightful drama is a modern-day retelling of Harlem Renaissance poet Langston Hughes' 1961 play "The Birth of Christ."
The Black Nativity, which released Wednesday nationwide, is set in the streets of Harlem, N.Y. The film centers on Langston (played by singer Jacob Latimore) who is sent to live with his estranged grandparents for the holidays. His mother, Naima (Jennifer Hudson), has not talked with her parents in 15 years, but was forced to send her son to live with them after she fell on hard financial times.
Langston's grandfather, the Rev. Cornell Cobbs (played by Forest Whitaker), has kept a shameful secret that he has been trying to overcome for years. As the film unfolds, you understand that this secret has caused his daughter, Niama, to move to Baltimore and rob Langston the opportunity to know his extended family.
Every year Langston's grandfather and grandmother (played by Angela Bassett), hold a church musical about the nativity story at the church they pastor. This section of the movie can soften even the hardest heart as the actors including Tyrese, Mary J. Blige and Hudson paint a gorgeous picture of Christ's birth and message of forgiveness with their colorful, rich vocals.
Throughout the film, Black Nativity beautifully weaves together themes of faith, family and forgiveness. Executive producer T.D. Jakes said it was important that honest, relatable stories of faith be brought to the big screen.
"The greatest star in this film is God because He's the one who ultimately pulls all of the pieces together," The Potter's House senior pastor said. "I think people who have ever seen God pull you out of the fire … almost every person has said at one time. 'Lord if you just get me out of this. I will never do it again. You will see that in this story."
From the singing to the dialogue, Christ is openly talked about and is even proclaimed in this family-friendly holiday flick.
Click below to watch Charisma interview Black Nativity producer T.D. Jakes and cast members Tyrese Gibson, Jacob Latimore, Mary J. Blige, Forest Whitaker and Angela Bassett.
Draw closer to God. Experience the presence of the Holy Spirit every month as you read Charisma magazine. Sign up now to get Charisma for as low as $1 per issue.
Get to know the Holy Spirit and how to interact with Him on a daily basis. Learn to enter God's presence and hear His voice clearly for yourself! Go deeper in your faith with Life in the Spirit and change your life and destiny. Are you ready to start your journey?


text:
FreeBSD General Other questions regarding FreeBSD which do not fit in any of the categories below. |
Thread Tools | Display Modes |
Constant Kernel Panics, Corupted file system reboots over and over
I am having some serious issues with what appears to be drive failures. However, this is a new drive. When I reisntall the system, it works perfectly fine for a few days, and then crashes with the error below. I have run smartctl -t long and no errors come up. After this crash, it rebooted twice and then came back up. I umounted the partition, did a fsck on it and it seemed to be working fine, for a few minutes. Then it crashed again and when the computer rebooted it couldn't find a valid boot partition. Luckly rebooting again into single user mode then running a fsck all all drives will bring it back up, temporarily.
Does anyone know what is going on here? What I am reading is that this an issue that has been known since 2004 but no one has bothered to fix. Something about softupdate being broken. System specs are FreeBSD 7.0 running on a Intell 1.66 GHz dual core with 2Gigs of DDR2, Intel (not sure model) motherboard with a Jmicron JMB363 controller. The log pasted below is the lastest crash. It also occurs when I put in ANY disk that isn't a member of an array. I have pasted in the logs from those crashes as well. ad8, ad10 and ad12 are all brand new and have no issues in any other computer. I am beginning to panic ATM there seems to be a path to bring the computer back up, but as time goes on, sooner or later it just isn't going to work. Any help you guys could give me would really be appreciated. Thanks ~m Most current crash: Jul 11 22:46:45 octavian kernel: ad8: FAILURE - device detached Crash 1: Jul 7 08:39:52 octavian fsck: /dev/ar0s1d: 3694 files, 352639422 used, 89402533 free (2053 frags, 11175060 blocks, 0.0% fragmentation) Last edited by pseudonym; 13th July 2008 at 02:02 AM. Reason: Wrong MB in hardware discription.. sorry.. have so many I lose track =P |
Thread Tools | |
Display Modes | |
Similar Threads | ||||
Thread | Thread Starter | Forum | Replies | Last Post |
kernel file from 6.3 to 7.2 | l2fl2f | FreeBSD Installation and Upgrading | 3 | 14th September 2009 06:53 PM |
File system not properly dismounted | rex | FreeBSD General | 6 | 12th September 2008 02:45 PM |
File system at more than 100% | michaelrmgreen | FreeBSD General | 4 | 28th July 2008 01:52 PM |
Kernel configuration file ignored? | FWS | FreeBSD Installation and Upgrading | 16 | 26th June 2008 10:28 AM |
Which file system use to share data on Bsd system? | aleunix | Other BSD and UNIX/UNIX-like | 2 | 1st June 2008 04:14 PM |


text:
Ah, see you are suffering from a lack of In'n'Out burger, I order you to smoke some meds, get some food, smoke high grade & eat. This should cure it.
I do , but i usually get a coffee going and a newspaper. Smoke a joint as i read my paper... actually thats my mornin routine.. will be hard to change that one. If i dont do that my day feels wrong haha. even if i only miss doing 1 of those 3 things... the spliff, newpaper, coffee... it bugs me
looks great...I'll add my balcony shot when it's not snowing lol Everyday thing though YouTube - Smoke DZA - Continental Kush Breakfast feat. Den10 (Dir. by Visually Inklined) [youtube]9DM580ippHg&hd=1[/youtube]


text:
2009-10 O-Pee-Chee Metal Hockey Card Preview
2009-10 O-Pee-Chee Metal Hockey is scheduled to release on 13 April and will cost about $65 per hobby box. Each box will contain 24 packs with each pack delivering five cards. Each pack will include two Metal Parallel. Find all cards from the 800 O-Pee-Chee card set to include all rookies that debuted in October (Tavares, Duchene, Philly's van Riemsdyk, Hedman, Kane, Leafs' Gustavsson, Del Zotto and more). Collectors can expect one Top Draws Triple Jersey cards and two Metal X version parallels per box. Each case will deliver two Hard-Signed Metal Autographs. Discuss this product in our Hockey Forum and get the best price OPC Metal boxes on eBay!
O-Pee-Chee Metal Parallels (combined to hit 2 per pack)
- OPC Metal (all 800 cards featured)
- OPC Metal X (all 800 cards featured) – inserted 1:12
O-Pee-Chee Update Variations
- OPC Retro Variation – inserted 1:1
- OPC Update Retro Variation, Rainbow parallel – #'d to 100
More Great Parallels
- OPC Update, Rainbow parallel – inserted 1:3
Triple Jersey Cards
- Top Draws – inserted 1:24
Signature Cards
- OPC Metal Autographs – inserted 1:144
- OPC Signatures {both inserts combine to drop 1:144}
- The Champions {both inserts combine to drop 1:144}
Regular Set
- 200 Regular/Marquee Rookie Cards
Print article | This entry was posted by admin on January 26, 2010 at 10:32 am, and is filed under NHL, O Pee Chee, Upper Deck. Follow any responses to this post through RSS 2.0. You can skip to the end and leave a response. Pinging is currently not allowed. |