To prevent playback of pirated, non-encrypted video, a DVD-based system examines data read from a DVD disk for MPEG-like characteristics. If such attributes are detected, the data is examined for the presence of a video usage-control watermark. The presence of such watermark indicates that the video should be distributed only in encrypted form, so playback of video from the disk is prevented.

The present invention relates to digital video, and more particularly relates to techniques for recognizing digital video so that certain usage-control systems may be implemented.
Certain applications would benefit from knowing whether a media-specific watermark is present in, effectively, a xe2x80x9cbucket of bits.xe2x80x9d In other words, one only knows, a priori, that one has a set of binary information, and even the very existence of a media objectxe2x80x94whether audio, video or still imagexe2x80x94is in question. It would be nice to first answer the question of whether a media object exists within this bucket of bits, followed by determining the specific form or format of that object (e.g., MPEG stream, JPEG image, BMP image, WAV file, etc.). Once the media object(if any) is characterized, it can be examined for a watermark. This disclosure provides a method for doing just this. It is presented in the harshest case of complete ignorance about the bucket of bits, whereas most practical applications will have additional knowledge about the data that can assist in correctly identifying its form and function, thus assisting in the watermark reading process.
Imagine we start with 10 Kilobytes of data randomly taken from any of the dozens of the digital physical media available (CD""s, DVD""s, Hard drives, memory, communication streams . . . anywhere at all). These bytes just show up on your doorstep somehow. You ask, is this a media object I should be interested in? And if so, is there a watermark in there?
Let""s begin with two extremes, one where it is generally impossible to figure out whether or not a media object is present and what its form is, and one where it is relatively straightforward. We will then move on to the gray area in between.
The xe2x80x9cimpossiblexe2x80x9d case is where some data object such as text, a program, a video, an image, whatever, has been encrypted using decent modern cryptographic methods. The essential point of cryptography is to not let some random person know what is xe2x80x9cwithin the data.xe2x80x9d Generally speaking, gross level characteristics and statistics of such data have been tidily swept clean and no discernable patterns can be found. The act of determining whether a watermark exists in such data is predicated upon specific breakdowns in cryptographic procedure, an area we will happily steer around in this disclosure and leave for braver souls.
On the other hand, one example of very many straightforward cases might be the following. A program is written simply to hunt for JPEG headers. Byte by byte, it simply walks through the whole bucket of bits and, bit by bit or byte by byte, simply xe2x80x9cassumesxe2x80x9d that a given bit or byte is the beginning of a JPEG header and sees if it can coherently decode the header using that bit/byte as a starting point, not quite knowing exactly where the ending point is. (Some headers have very precise lengths, speaking to this latter point about not knowing how long it is). As with the millions of monkeys typing on their keyboards eventually producing Hamlet, every now and then this program will think it has found a valid header when it has indeed found garbage, but it can then either begin to look for telltale huffman streams and refine its ability to recognize a JPEG image, or, more simply, it can simply not care it might be finding garbage and invoke a watermark reading process on xe2x80x9cpresumedxe2x80x9d JPEG data. The worst that can happen is that no watermark is found or read.
(The present technology is applicable with any digital watermarking technique; exemplary watermarking techniques are disclosed in U.S. Pat. Nos. 5,832,119, 5,825,892, and 5,915,027.)
In this simpler case of looking for a JPEG header, the process of reading a watermark from this initially unknown bucket of bits is then to simply run the JPEG header-hunter routine followed by any standard watermark reading routine. End of story.
Let""s now look at some more difficult cases and attempt to specify certain operations that could underpin any generalized watermark reader on generalized unknown data.
Let""s look at the case of an MPEG stream where it may be impractical to xe2x80x9csearch for telltale headers.xe2x80x9d It might even be that a non-crytpographic-grade scrambling function has been applied to the pure MPEG stream, i.e., a scrambling function which is meant to stop average consumers from co-opting materials but certainly has no pretensions of stopping cryptographic pro""s.
In the non-scrambled version, a xe2x80x9crandom sampling watermark detectorxe2x80x9d can be built which basically operates on some small but non-trivial xe2x80x9cchunkxe2x80x9d of data, essentially asking a series of questions all revolving around the basic question of xe2x80x9cdo you have MPEG-like data structures.xe2x80x9d Examples include: xe2x80x9care there data structures which resemble sequences of macroblocks, with subsequences of 4 blocks within the macroblocks.xe2x80x9d More specifically, and similar to the JPEG header-hunter, the existence of macroblocks can be assumed, but with an unknown xe2x80x9cstart point;xe2x80x9d many trial start points can be tried and some start points (followed by typical decoding steps associated with MPEG/Huffman decoding) will start to produce what appear to be true macroblock data. Options include assuming it is indeed macroblock data and attempting watermark reading, but more likely other questions will be asked of the data before the step of watermark reading is invoked.
Returning back to the xe2x80x9cdo you have MPEG-like data structuresxe2x80x9d issue then, another example might include looking for interframe sub-header data structures as well, or looking for these only if an earlier step thinks it might be seeing true macroblock data. One can also treat raw ones and zeros of the data stream as a time waveform and look at is spectral and statistical properties and look for xe2x80x9cMPEG class signaturesxe2x80x9d within these transformed spaces.
In any event, once some reasonable level of confidence is obtained that an MPEG object exists within the bucket of bits and once some general notion of where macroblocks are synchronized, a watermark reading routine can be invoked and a xe2x80x9cpositive readxe2x80x9d (in the case where false positives are pre-designed to be very unlikely) is the best way of making sure that an object is an MPEG object.
One final note on the non-scrambled MPEG case, the xe2x80x9cdo you have MPEG-like data structuresxe2x80x9d questions can be seen as distinct modules, each with a probability attached. These modules can be stacked in order to gain sufficient confidence that an MPEG stream is present. Furthermore, interim states of confidence can invoke grabbing of more data and reapplying the question modules to more data if a sufficient level of confidence is not reached right away. The issue here gets down to xe2x80x9cwhich is computationally cheaper,xe2x80x9d getting more data and building confidence, or simply going for a full watermark read routine.
Moving on to the scrambled MPEG video case, a similar philosophy of asking a set of modularized questions can be used, only they will be much more along the classic cryptographic analysis lines than in the non-scrambled case which can search for specific structures. Furthermore, presumably most applications which intend to look for these scrambled signals will also have the means to unscramble the data if a scrambled stream is indeed found. Building in the means to xe2x80x9csleuth the scramblingxe2x80x9d is certainly not an intent of this disclosure. Implicit in all of this is that the process to xe2x80x9cdescramble the signal using all arbitrary starting pointsxe2x80x9d is computationally more expensive than the process to ask the questions xe2x80x9cdo you have scrambled MPEG-like data characteristics.xe2x80x9d Key words have changed in this phrasing of the question.
In the scrambled case, then, we find a three step process: 1) look for scrambled MPEG signal characteristics, including looking for specific commercial flavors of scrambling; 2) descramble the data if a certain confidence level is reached in number 1, where one may need to grab more data if the initial chunk grabbed is insufficient for descrambling; then 3) invoke any given watermark reading routines properly synchronized to the macroblocks (which is assumed to be feasible due to the proper descrambling method being used in step 2).
Generalizing all of this to arbitrary media objects, not just JPEG and MPEG, any given target media type would have their question modules with procedures tuned to characteristics and structures unique to their specific type/format. Question modules (sometimes just one) are stacked and applied to the bucket of bits. Confidence levels either remain low or begin to peak when a given media object being searched for starts showing up in the bucket of bits. Then watermark reading routines are invoked, routines associated with the given media object that is showing up on the confidence radar screen.
Generalizing this yet further, these techniques can be applied to the time waveform of data into and out from a CPU or any digital node within a digital system. The question modules, the decoding (descrambling) modules, and the watermark types can all be tuned to a given node, and a generalized watermark reader can effectively watch digital traffic go by, then potentially add value to consumers who want to enable certain operations connected to certain watermarked media objects, or can add value to copyright holders who have every intent to retain their rights to their material and ensure that any uses of their material have been properly paid for or permitted.
One particular application of such technology is as an adjunct to a copy protection system for digital video. A variety of such systems are known, as illustrated by U.S. Pat. Nos. 5,915,018, 5,949,877, 5,923,754, and 5,883,958, and by the Content Scrambling System (CSS), licensed by Matsushita. Video distributed in accordance with the CSS standard is encrypted for storage on a DVD disk. Playback devices encountering such CSS-encrypted data must have CSS decryption hardware or software for the playback to proceed. Matsushita is working to incorporate a digital watermark component to provide further playback and copy control features. Two industry consortia, one composed of the present assignee, Macrovision and NV Philips, and the other composed of IBM, NEC, Hitachi, Sony and Pioneer, have proposed specific watermarking systems that may be suitable. (See www.dvcc.com/warp for specifics of the proposals.) For expository convenience, such watermarking systems are here called CSS watermarking systems.
A problem arises, however, if a hacker gains access to the un-encrypted video, e.g., by intercepting the analog drive signals fed to the display device. Such video signals can be re-digitized, and stored on writable media (the writable DVD is not far off) for playback without CSS constraints. Such pirated video clearly poses a large economic threat to Hollywood and other content providers. However, such video would still include the CSS watermark and, if the non-CSS-encoded data being read from a DVD disk can be recognized as MPEG video, a watermark detection operation can be invoked.
Desirably, then, generic DVD drives are provided with built-in hardware or firmware that checks the raw data read from the disk for MPEG-like characteristics. (The details of prior art DVD drives are familiar to the artisan and are not belabored here.) If suspected MPEG data is identified, the hardware and/or firmware invokes a watermark reading operation (which may also be integrated with the drive, or external to it, and may be implemented in hardware, firmware, or software) to see if the data carries a CSS watermark. (This operation may, or may not, require full or partial decoding of the MPEG data stream. A wide variety of techniques for detecting watermarks from MPEG data streams are known.) If such a watermark is detected, the hardware and/or firmware can simply interrupt the read operation, or the provision of data on the output bus; no CSS watermarked video should be encountered on a DVD that is not CSS-encrypted.
It will be recognized that it is not always necessary to read (decode) the watermark. Once the presence of a CSS watermark has been detected, its data payload is substantially irrelevant. Often, implementation can be simplified (e.g., gate count can be reduced, or MIPs processing burden can be be lessened) by skipping the final decoding steps once the watermark""s presence has been ascertained.
To avoid certain hacks, the MPEG-detection system may be arranged to work on out-of-order sectors of data, in case the disk is read non-sequentially. Similarly, the system may be arranged to check for simple data inversion in its screening of the DVD data for possible MPEG video.
FIG. 1 shows such a system 10 that includes a sensor 14 for reading data from a DVD disc 12, an MPEG screening system 16, and a watermark sensor 18 (e.g., watermark reader) responsive to the output of the MPEG screening system. Desirably, these components 14-18 are provided as part of a DVD drive unit.
FIG. 2 shows a method 20 that may be performed by the system 10 of FIG. 1. Data is read from the storage medium (22) and is examined for one or more attributes associated with MPEG video (24). If such attribute is found (26), the process next determines whether a watermark is present (28). If so (30), the system responds by preventing playback (32).
To provide a comprehensive disclosure without unduly lengthening this specification, the above-cited patents are incorporated by reference.

Methods for reading watermarks in unknown data types, and DVD drives with such functionality


A method of processing a photographic imaging element to obtain a protective overcoat is disclosed, which overcoat provides, in the final product, resistance to fingerprints, common stains, and spills. More particularly, the present invention involves a processing-solution-permeable overcoat that becomes water and stain resistant in the photochemically processed product. The overcoat formulation comprises at least one water-dispersible hydrophobic polymer interspersed with a water-soluble polymer. During development or thereafter, before drying, the water-soluble polymer is removed to a significant extent. Subsequently, the imaged element is dried at an elevated temperature to facilitate coalescence of the overcoat to thereby provide enhanced stain resistance and water-resistance.

The present invention relates to a method of processing a photographic imaging element to obtain a protective overcoat that provides resistance to fingerprints, common stains, and spills. The overcoat formulation comprises at least one water-dispersible hydrophobic polymer interspersed with a water-soluble polymer. The imaged photographic element is dried at an elevated temperature to facilitate coalescence of the hydrophobic polymer in the overcoat, thereby providing enhanced stain resistance and water resistance.
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 dye forming compound called a coupler. 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 or similar natural or synthetic hydrophilic polymers have proven to be the binders of choice for silver halide photographic elements. Unfortunately, when gelatin or similar polymers are formulated so as to facilitate contact between the silver halide crystals and aqueous processing solutions, the resultant coatings are not as fingerprint and stain resistant as would be desirable, particularly in view of the handling or environment that an imaged photographic element may commonly experience at various times and circumstances. Thus, fingerprints can permanently mark the imaged element. The imaged element can be easily stained by common household products, such as foods or beverages, for example, coffee spills.
There have been attempts over the years to provide protective layers for gelatin based photographic systems that will protect the images from damages 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. Various lamination techniques are known and practiced in the trade. U.S. Pat. Nos. 3,397,980, 3,697,277 and 4,999,266 describe methods of laminating a polymeric sheet film, as a protective layer, on a processed image.
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. Thus, the processing equipment needs to be modified and the personnel running the processing operation need to be trained to apply the protective coating. 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. 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. Again, however, the hydrophobic polymer particles must be fused to form a protective coating that is continuous and water-impermeable.
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 200xc2x0 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. Again, however, fusing is required by the photofinishing laboratories to render the protective overcoat water-resistant. Similarly, commonly assigned U.S. Ser. No. 09/353,939 and U.S. Ser. No. 09/548,514, respectively, describe the use of a polystyrene-based material and a polyurethane-based material, with gelatin as the binder, in an overcoat for a photographic element, which overcoat can be fused into a water resistant overcoat after photographic processing is accomplished to generate an image.
Commonly assigned U.S. Ser. No. 09/235,436 discloses the use of a processing solution permeable overcoat that is composed of a urethane-vinyl copolymer having acid functionalities. Commonly assigned U.S. Ser. No. 09/235,437 and U.S. Pat. No. 6,194,130 B1 disclose the use of a second polymer such as a gelatin or polyvinyl alcohol to improve processibility and reduce coating defects. Commonly assigned U.S. Ser. No. 09/621,267 discloses the use of a processing solution permeable overcoat that is composed of various non-gelatin containing water-dispersible polymers in combination with a water-soluble polymer.
While the prior art has disclosed imaging elements with a processing permeable overcoat that is rendered water impermeable, and the materials used to prepare such overcoats, it has not been specific in how these imaging elements have been prepared. The desired overcoat may be applied in several possible methods. It may be applied to a imaging element that is previously coated with all layers except the overcoat. In such a case, the overcoat may be applied as a single layer. It also could be applied in a single coating operation, in a tandem method. In this case all the layers, except the desired overcoat can be applied at a first station in the coating machine. The web is then dried and run through a second coating station, without winding it up, where the overcoat is applied.
The most preferred method for coating an overcoat is at a single coating station, along with the other imaging layers. This is typically accomplished with gelatin overcoats using a slide hopper where multiple solutions are layered without mixing. The layered solutions are then deposited on the web either by bead coating or by dropping it as a curtain onto the web.
A polymeric latex protective overcoat when coated simultaneously with underlying emulsion layers in a so-called single pass operation, during manufacture of a photographic imaging element, has been found not to deliver the same stain protection features observed when coated separately in a so-called xe2x80x9ctwo-passxe2x80x9d coating operation. Thus, it has been found that the functionality of the overcoats employed in the present invention, with specific reference to its water permeability, can be different depending on whether the polymer layer is coated simultaneously with the imaging layers or in a separate process step. In the simultaneous coating method, the solution of the water-dispersible and water-soluble polymer is in fluid contact with a solution containing the imaging chemistry and its hydrophilic binder (usually, gelatin). It is found that the stain resistance and water permeability of the overcoat applied in this manner, is greatly diminished. Without being bound by theory, it is believed that some water soluble components from the adjacent imaging layers travel to the overcoat and, thus, making it difficult for the polymer latexes to form a continuous film and, thereby, preventing or decreasing coalescence of the latex in the final imaged product.
It would be desirable to obtain an imaging element comprising an overcoat that is process-permeable during photoprocessing and which can be converted to a water-resistant protective overcoat for the imaged element, which water resistance is not lost or decreased when the overcoat is simultaneously coated with the emulsion layers. It would be further desirable if this could be accomplished without the addition of laminating or fusing steps, without the need for high temperature fusing, and preferably with minimal or no additional equipment to carry out photoprocessing
The present invention provides a method of forming an image in an imaging element and converting the overcoat into a water-resistant coating. In particular, it has been found that stain resistance and/or water resistance of an imaged element having a protective overcoat can be obtained or enhanced, when the overcoat (nascently protective) is coated simultaneously with the gelatin-based emulsion layers, by subjecting the product, after it emerges from the last photoprocessing step, to an elevated temperature, above 160xc2x0 F. for a given period of time This can involve a sustained period of time beyond minimal drying of the photographic element, such that the temperature of photographic element can reach or approach said elevated temperature. This drying of the image element at elevated temperatures facilitates coalescence of the latex in the overcoat, thus rendering the product more resistant to staining and/or water.
The imaged element processed according to the present invention comprises a processing-solution-permeable overcoat for a photographic element. For example, such a photographic element may comprise a support, at least one silver-halide emulsion layer superposed on the support, and overlying the silver-halide emulsion layer, a processing-solution-permeable protective overcoat composition that can be incorporated into or coated on the imaging element during manufacturing and that does not inhibit photographic processing. A component of the invention are polymer particles that are water-dispersible. The material of the invention can be introduced to the overcoat coating melt in a latex form or as a conventional colloidal dispersion in a water-soluble binder. The presence of a water-soluble component that is substantially washed out during processing allows photographic processing to proceed at an acceptable rate. The washing out of the water-soluble component facilitates the coalescence of the water-dispersible materials to form a water resistant continuous layer in the final product.
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 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 between xe2x88x9240 and 80xc2x0 C. In general, the overcoat composition preferably contains a water-soluble, hydrophilic polymer that is typically noncrosslinked to facilitate its washing out during processing and, at least to some extent, to facilitate the coalescence of the water-dispersible polymer particles. Preferably, the overcoat formulation is substantially gelatin-free, comprising less than 5% crosslinked gelatin by weight of solids.
In another embodiment of the invention, the overcoat composition applied to the imaging element comprises 5 to 70% by weight of solids of water-soluble hydrophilic polymer such that more than 30 weight percent of the water-soluble polymer is washed out during photographic processing; wherein the weight ratio of the water-dispersible polymer to the non-crosslinked water-soluble polymer is between 60:40 to 85:15 and whereby the overcoat forms a water-resistant overcoat after photoprocessing without fusing.
The present invention provides a simple and inexpensive way to improve the water, stain and abrasion resistance of processed photographic elements. In accordance with the invention, the protective overcoat is applied over the photographic element prior to exposure and processing. In particular, a overcoat formulation according to the present invention is applied to the emulsion side of photographic products, particularly photographic prints, which may encounter frequent handling and abuse by end users.
By the term xe2x80x9cwater-resistantxe2x80x9d is meant herein after ordinary photoprocessing and drying does not imbibe water or prevents or minimizes water-based stains from discoloring the imaged side of the photographic element. By the term xe2x80x9cnon-crosslinked gelatinxe2x80x9d is meant gelatin that is water soluble.
By the term xe2x80x9celevated temperaturexe2x80x9d, as used in this application, to dry and/or facilitate coalescence of the water-dispersible polymer, is herein meant a temperature of greater than 160xc2x0 F., preferably between 160 and 212xc2x0 F., more preferably 170 to 200xc2x0 F., most preferably 180 to 195xc2x0 F. In contrast, fusing typically requires a pressure roller or belt and drying of the imaged element before fusing. In contrast, fusing, which involves simultaneously applied heat and pressure, for example by means of a nip between two rollers, generally requires higher temperatures, typically above the boiling point of water, usually above 100xc2x0 C. For that reason, fusing normally is applied to an imaged element only after drying.
The heating step according to the present method cannot be applied prior to the typical processing sequence (involving, for example, the three steps of developing, bleach-fixing, and washing), whether the imaging element is heated dry or in the presence of a water film. In other words, when the water-soluble polymer is still in the coating (the water film does not allow the water-soluble polymer to exit the overcoat), the desired stain resistance enhancement cannot be achieved by high temperature heating. Similarly, if the imaging element is dried mildly after the processing, for example, after washing, and the high temperature treatment is then applied to a dried film, the enhanced stain resistance cannot be achieved. Thus, the high temperature treatment has to be applied to the imaging element, while it is wet, after it has gone through the three processing steps mentioned above. Preferably, the elevated temperature needs to be applied to the photographic element when it is at least 100% saturated with water.
The results show that a wide variety of water-dispersible polymers respond favorably to the high temperature drying after processing in accordance with the present method. It is preferred that the Tg of the polymers be below 100xc2x0 C. in order to respond most favorably to the high temperature drying. In a preferred embodiment the polymeric overcoat, materials comprises polyester ionomers such as AQ-55(copyright) polyester manufactured by Eastman Chemical (Tgxe2x80x9455xc2x0 C.), dispersed polyurethane lattices, NEOCRYL acrylic polymers manufactured by Zeneca, acrylic/urethane interpenetrating polymers, and the like, disclosed for example in commonly assigned patent applications U.S. Pat. No. 6,077,648, U.S. Ser. No. 09/235,437 U.S. Pat. No. 6,194,130 B1, U.S. Ser. No. 09/621,267, hereby incorporated by reference in their entirety.
In typical large scale photofinishing machines, the dryer settings can vary, depending on the length of the drier and the load (amount of material to be dried). If the length is short and/or the load is heavy, higher temperatures are typically used. However, because of the cost of drying energy, the driers are usually set, such that the product emerges just dry from the machine. In such operations, even though the drier temperature can be fairly high, the actual temperature that the wet web experiences is low, due to the high wet load. In conventional commercial practice, the typical temperature range is from 125-150xc2x0 F.
Typically, traditional photoprocessing equipment can employ a wide variety of different dryers. Almost exclusively, however, the dryers operate by convective heating. That is, a heater is used to heat the air going into the dryer. This lowers the relative humidity of the air, which is then circulated by blowing it through the dryer sections. Several modes of circulation may be employed: co-current or counter-current to the direction of the web, or in a random fashion. Depending on the length of the dryer and the throughput of the web, the temperature of the air entering the dryer can be varied. The faster the drying rate desired, the higher will be the temperature of the air. Although, in the trade the temperatures presently employed typically range from 125xc2x0 F. to 150xc2x0 F., the temperature and residence time can be adjusted in accordance with the present invention.
Although convective drying is almost exclusively practiced in conventional equipment, other means of drying may be devised for use in the present invention. These include heating belts, high temperature radiant sources or even by employing a mild vacuum. The most practical of these is to employ a radiant heat source. A radiant heat source can be placed next to the path of the web in the dryer. When the web passes by the heating source, the web temperature is raised, thereby driving the residual water from the web. Although, it is hard to measure a temperature of a radiant heat source, the most relevant temperature is the temperature that the web reaches. This can be measured by sticking a temperature sensitive label on the web. A combination of a convective drying and radiant drying can also be used, particularly to apply the higher temperature to facilitate latex coalescence towards the end of the drying cycle.
In a preferred embodiment, the dryer comprises both a convective heat section and a radiant heat section. Both heating sections heat from top and bottom. The convective heat section comprises a plurality of air vents on top and bottom, whereby hot air is blown through the vents onto the coating. Typically, there are two sets of rollers on each end of this section to move the coating through the dryer, and roller speed can be controlled in the range of about 0-3 inches per second. In a preferred embodiment, the radiant heat section comprises a quartz radiant heating tube on top and one below. A cabinet type dryer that has hot air circulating can also be used.
In one embodiment, the photographic element is dried at the above-mentioned average elevated temperature for a period of time of 1 sec to 2 minutes, preferably 2 to 30 seconds, most preferably between 4 and 10 seconds. Because the drying is designed to provide heat treatment beyond the minimum amount of drying (beyond just dry), the temperature of the surface of the photographic element can achieve a relatively higher temperature than in a conventional photoprocessing drying. The temperature of the photographic element is preferably within 10xc2x0 F., more preferably within 5xc2x0 F. of the maximum temperature of the dryer to which the photographic element is exposed. Preferably, the moisture content should be less than 15% of the weight of the dried coating (not including support).
As indicated above, the preferred overcoat formulation used in this invention comprises 30 to 95% by weight (based on the dry laydown of the overcoat) of water-dispersible polymer particles of 0.01 to 0.5 micrometers in average size and 5 to 70% by weight of a water-soluble polymer which is substantially uncrosslinked (based on the dry laydown of the overcoat). The use of less than 5% by weight of crosslinked gelatin or other crosslinked water-soluble polymer in the overcoat (as applied) promotes coalescence during the heating step. It is noted that some gelatin from underlying layers in the photographic element may migrate into the overcoat, during manufacture or photochemical processing, for example, but any such migration is limited and, by definition, is not included in the described composition formulation or in the applied overcoat. In one embodiment, less than 5%, more preferably less than 3%, by weight of solids, of gelatin is included in the overcoat composition. Most preferably, essentially no gelatin is included in the overcoat formulation.
In another preferred embodiment, the present method involves a method of making and processing a photographic element that comprises: (a) a support; (b) at least one silver-halide emulsion layer superposed on a side of said support; and (c) overlying the silver emulsion layer, a processing-solution-permeable protective overcoat having a laydown of at least 0.54 g/m2 (50 mg/ft2) made from a formulation comprising less than 5%, by weight of solids, of crosslinked gelatin and further comprising 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 between xe2x88x9240 to 80xc2x0 C., preferably 10xc2x0 C. to 60xc2x0 C., and 5 to 70%, by weight of solids, preferably 10 to 40 weight percent, of a water-soluble hydrophilic polymer such that more than 30 weight percent of the water-soluble polymer is washed out during photographic processing; wherein the weight ratio of the water-dispersible polymer to the non-crosslinked water-soluble polymer is between 50:50 to 90:10, preferably 60:40 to 85:15, whereby the overcoat forms a water-resistant overcoat after photoprocessing without fusing, namely by maintaining the photographic element at temperature less than 100xc2x0 C.
The dispersions of water-dispersible polymers used in this invention are latexes or polymers of any composition that can be stabilized in an water-based medium. Such water-dispersible polymers are generally classified as either condensation polymer or addition polymers. Condensation polymers include, for example, polyesters, polyamides, polyurethanes, polyureas, polyethers, polycarbonates, polyacid anhydrides, and polymers comprising combinations of the above-mentioned types. Addition polymers are polymers formed from polymerization of vinyl-type monomers including, for example, allyl compounds, vinyl ethers, vinyl heterocyclic compounds, styrenes, olefins and halogenated olefins, unsaturated acids and esters derived form them, unsaturated nitriles, acrylamides and methacrylamides, vinyl ketones, multifunctional monomers, or copolymers formed from various combinations of these monomers. Such latex polymers can be prepared in aqueous media using well-known free radical emulsion polymerization methods and may consist of homopolymers made from one type of the above-mentioned monomers or copolymers made from more than one type of the above-mentioned monomers. Polymers comprising monomers which form water-insoluble homopolymers are preferred, as are copolymers of such monomers. Preferred polymers may also comprise monomers which give water-soluble homopolymers, if the overall polymer composition is sufficiently water-insoluble to form a latex. Further listings of suitable monomers for addition type polymers are found in U.S. pat. No. 5,594,047 incorporated herein by reference. The polymer can be prepared by emulsion polymerization, solution polymerization, suspension polymerization, dispersion polymerization, ionic polymerization (cationic, anionic), Atomic Transfer Radical Polymerization, and other polymerization methods known in the art of polymerization. The selection of water-dispersible particles to be used in the overcoat is based on the material properties one wishes to have as the protective overcoat in addition to water resistance.
The water-dispersible polymer is selected so that fusing is not required, a potentially significant advantage compared to the prior art, for example U.S. Pat. No. 5,856,051, mentioned above.
In a preferred embodiment of the invention, the water-dispersible polymer is a substantially amorphous, thermoplastic polymer having ionized or ionizable groups or moieties in sufficient number to provide water dispersibility prior to coating. In addition to water-resistance, the polymer dispersions in the finally processed product preferably provides further advantageous properties such as good chemical and stain resistance, wet-abrasion resistance, fingerprint resistance, toughness, elasticity, durability, and/or resistance to various oils.
In the case of carboxylic acid ionic groups, the polymer can be characterized by the acid number, which is preferably greater than or equal to 5 and relatively permeable to water at a pH of greater than 7. Preferably, the acid number is less than or equal to 40, more preferably less than or equal to 30. Preferably, the pH of the developing solution is greater than 8, preferably greater than 9. The water-reducible water-dispersible polymer particles comprising ionized or ionizable groups may be branched, unbranched, crosslinked, uncrosslinked.
In accordance with this invention, the protective overcoat preferably comprises, in addition to the water-dispersible polymer described above, at least one water-soluble hydrophilic polymer. Examples of such water-soluble polymers that may be added include polyvinyl alcohol, cellulose ethers, poly(N-vinyl amides), polyacrylamides, polyesters, poly(ethylene oxide), dextrans, starch, uncrosslinked gelatin, 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 xe2x80x9cHandbook of Water-Soluble Gums and Resinsxe2x80x9d by Robert 1. Davidson (McGraw-Hill Book Company, 1980) or xe2x80x9cOrganic Colloidsxe2x80x9d by Bruno Jirgensons (Elsvier Publishing Company, 1958). In a preferred embodiment, the polymer is polyvinyl alcohol, 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.
The preferred water-soluble polymer is polyvinyl alcohol. The term xe2x80x9cpolyvinyl alcoholxe2x80x9d referred to herein means a polymer having a monomer unit of vinyl alcohol as a main component. Polyvinyl alcohol is typically prepared by substantial hydrolysis of polyvinyl acetate. Such a xe2x80x9cpolyvinyl alcoholxe2x80x9d includes, for example, a polymer obtained by hydrolyzing (saponifying) the acetate ester portion of a vinyl acetate polymer (exactly, a polymer in which a copolymer of vinyl alcohol and vinyl acetate is formed), and polymers obtained by saponifying a trifluorovinylacetate polymer, a vinyl formate polymer, a vinyl pivalate polymer, a tert-butylvinylether polymer, a trimethylsilylvinylether polymer, and the like (the details of xe2x80x9cpolyvinyl alcoholxe2x80x9d can be referred to, for example, xe2x80x9cWorld of PVAxe2x80x9d, Edited by the Poval Society and Published by Kobunshi Kankoukai, Japan, 1992 and xe2x80x9cPovalxe2x80x9d, Edited by Nagano et al. and Published by Kobunshi Kankoukai, Japan, 1981). The degree of hydrolysis (or saponification) in the polyvinyl alcohol is preferably at least about 70% or more, more preferably at least about 80%. Percent hydrolysis refers to mole percent. For example, a degree of hydrolysis of 90% refers to polymers in which 90 mol % of all copolymerized monomer units of the polymer are vinyl alcohol units. The remainder of all monomer units consists of monomer units such as ethylene, vinyl acetate, vinyl trifluoroacetate and other comonomer units which are known for such copolymers. Most preferably, the polyvinyl alcohol has a weight average molecular weight (MW) of less than 150,000, preferably less than 100,000, and a degree of hydrolysis greater than 70%. If the MW is greater than 100,000, the degree of hydrolysis is preferably less than 95%. Preferably, the degree of hydrolysis is 85 to 90% for a polyvinyl alcohol having a weight average MW of 25,000 to 75,000. These preferred limitations may provide improved manufacturability and processibility. The polyvinyl alcohol is selected to make the coating wettable, readily processable, and in a substantial amount, to readily, not sluggishly, come out of the coating during processing, thereby yielding the final water-resistant product. The optimal amount of polyvinyl alcohol depends on the amount of dry coverage of water-dispersible polymer. In one preferred embodiment of the invention, the polyvinyl alcohol is present in the overcoat in the amount between 1 and 60 weight percent of the water-dispersible polymer, preferably between 5 and 50 weight percent of the water-dispersible polymer, most preferably between 10 and 45 weight percent of the water-dispersible polymer.
Without being bound by theory, it is believed that the water-soluble polymer and water-dispersible polymer form a compatible mixture, which allows the formation of a water-resistant overcoat that does not require fusing, merely elevated temperatures preferably up to about 60xc2x0 C. It is believed that fusing is not required for several reasons: (a) the substantial absence of cross-linked gelatin and other such crosslinked polymers, and (b) the selection of a water-dispersible polymer that is believed to form a compatible mixture with the hydrophilic water-soluble polymer, c) the selection of the water soluble polymer which is believed to be removed during processing such that the water dispersible polymer coalesces to form a continuous water-resistant overcoat.
Optionally, the coating composition in accordance with the invention may also contain suitable crosslinking agents for crosslinking the water-dispersible polymer. Such an additive can improve the adhesion of the overcoat layer to the substrate below as well as contribute to the cohesive strength of the layer. Crosslinkers such as epoxy compounds, polyfunctional aziridines, methoxyalkyl melamines, triazines, polyisocyanates, carbodiimides, polyvalent metal cations, and the like may all be considered. If a crosslinker is added, care must be taken that excessive amounts are not used as this will decrease the permeability of the processing solution. The crosslinker may be added to the mixture of water-dispersible component and any additional polymers.
The optimal amount of the water-soluble polymer may depend on the amount of dry coverage of water-dispersible polymer. For example, in the case of the combination of a polyurethane polymer and a polyvinyl alcohol polymer, if coverage of a polyurethane polymer is 1.08 g/m2 (100 mg/ft2) or less, then about 20% or less of polyvinyl alcohol, by weight of the polyurethane, provides good results, whereas for higher coverage, for example (1.88 g/m2) 175 mg/ft2, greater than about 25% of the polyvinyl alcohol provides comparably good results.
In one preferred embodiment, the water-dispersible polymer of this invention are polyurethanes, preferably segmented polyurethanes. Polyurethanes are the polymerization reaction product of a mixture comprising polyol monomers and polyisocyanate monomers.
A preferred segmented polyurethane is described schematically by the following structure (I):
wherein R1 is preferably a hydrocarbon group having a valence of two, more preferably containing a substituted or unsubstituted, cyclic or non-cyclic, aliphatic or aromatic group, most preferably represented by one or more of the following structures:
and wherein A represents a polyol, such as a) a dihydroxy polyester obtained by esterification of a dicarboxylic acid such as succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic, isophthalic, terephthalic, tetrahydrophthalic acid, and the like, and a diol such as ethylene glycol, propylene-1,2-glycol, propylene-1,3-glycol, diethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol, neopentyl glycol, 2-methyl propane-1,3-diol, or the various isomeric bis-hydroxymethylcyclohexanes; b) a polylactone such as polymers of xcex5-caprolactone and one of the above mentioned diols; c) a polycarbonate obtained, for example, by reacting one of the above-mentioned diols with diaryl carbonates or phosgene; or d) a polyether such as a polymer or copolymer of styrene oxide, propylene oxide, tetrahydrofuran, butylene oxide or epichlorohydrin;
R3 is a phosphonate, carboxylate or sulfonate group; and.
R2 is a diamine or diol having a molecular weight less than about 500. Suitable well known diamine chain extenders useful herein include ethylene diamine, diethylene triamine, propylene diamine, butylene diamine, hexamethylene diamine, cyclohexylene diamine, phenylene diamine, tolylene diamine, xylylene diamine, 3,3xe2x80x2-dinitrobenzidene, ethylene methylenebis(2-chloroaniline), 3,3xe2x80x2-dichloro-4,4xe2x80x2-biphenyl diamine. 2,6-diaminopyridine, 4,4xe2x80x2-diamino diphenylmethane, and adducts of diethylene triamine with acrylate or its hydrolyzed products. Also included are materials such as hydrazine, substituted hydrazines such as, for example, dimethyl hydrazine, 1,6-hexamethylene-bis-hydrazine, carbodihydrazide, hydrazides of dicarboxylic acids and sulfonic acids such as adipic acid mono- or dihydrazide, oxalic acid dihydrazide, isophthalic acid dihydrazide, tartaric acid dihydrazide, 1,3-phenylene disulfonic acid dihydrazide, omega-amino-caproic acid dihydrazide, hydrazides made by reacting lactones with hydrazine such as gamma-hydroxylbutyric hydrazide, bis-semi-carbazide, bis-hydrazide carbonic esters of glycols such as any of the glycols mentioned above. Suitable well known diol chain extenders may be any of the glycols or diols listed above for A. R3 is a phosphonate, carboxylate or sulfonate group.
The number of repeating units of Structure I can range from 2 to 200, preferably 20 to 100. The amount of the hard-segment (in the right-hand parenthesis)is preferably 40 to 70 percent by weight. The weight ratio of the OR3O to the OR2O repeating unit preferably varies from 0 to 0.1. The water-dispersible polyurethane employed in the invention may be prepared as described in xe2x80x9cPolyurethane Handbookxe2x80x9d, Hanser Publishers, Munich Vienna, 1985.
The term xe2x80x9cpolyurethanexe2x80x9d, as used herein, includes branched and unbranched copolymers, as well as IPN and semi-IPNs comprising at least two polymers, at least one of which is a polyurethane.
An IPN is an intimate combination of two or two or more polymers in a network, involving essentially(that may essentially involve) no covalent bonds or grafts between them. Instead, these intimate mixtures of polymers are held together by permanent entanglements produced when at least one of the polymers is synthesized in the presence of the other. Since there is usually molecular interpenetration of the polymers in IPNs, they tend to phase separate less compared to blends. Such interpenetrating polymer network systems and developments are described by L. H. Sperling in xe2x80x9cInterpenetrating Polymer Networks and Related Materials,xe2x80x9d Plenum Press, New York, 1981, in pages 21-56 of xe2x80x9cMulticomponent Polymer Materialsxe2x80x9d ACS Adv. In Chem. No. 211, edited by D. R. Paul and L. H. Sperling, ACS Books, Washington, D.C., 1986, and in pages 423-436 of xe2x80x9cComprehensive Polymer Sciencexe2x80x9d, Volume 6, xe2x80x9cPolymer Reactionsxe2x80x9d, edited by G. C. Eastmond, A. Ledwith, S. Russo, and P. Sigwalt, Pergamon Press, Elmsford, N.Y., 1989. While an ideal structure may involve optimal interpenetration, it is recognized that in practice phase separation may limit actual molecular interpenetration. Thus, an IPN may be described as having xe2x80x9cinterpenetrating phasesxe2x80x9d and/or xe2x80x9cinterpenetrating networks.xe2x80x9d If the synthesis or crosslinking of two or more of the constituent components is concurrent, the system may be designated a simultaneous interpenetrating network. If on the other hand, the synthesis and/or crosslinking are carried out separately, the system may be designated a sequential interpenetrating polymer network. A polymer system comprising two or more constituent polymers in intimate contact, wherein at least one is crosslinked and at least one other is linear is designated a semi-interpenetrating polymer network. For example, this type of polymer system has been formed in cured photopolymerizable systems such as disclosed in Chapter 7 of xe2x80x9cImaging Processes and Materials-Neblette""s Eighth Edition,xe2x80x9d edited by J. M. Sturge, V. Walworth and A. Shepp, Van Nostrand Reinhold, New York, 1989.
In one embodiment of the present invention, the water-dispersible polymer is a polyurethane containing pH responsive groups such as acid functionalities and have an acid number greater than or equal to 5, preferably less than or equal to 40, more preferably less than or equal to 30, most preferably from 10 to 25. The weight ratio of the optional vinyl polymer in the polymer can vary from 0 to 80 percent, including a interpenetrating network of a urethane polymer and a vinyl polymer if the amount of vinyl polymer is substantially greater than zero.
In another embodiment of the present invention, the water-dispersible polymer is a polyurethane-containing component that is an IPN or semi-IPN comprising a polyurethane and a vinyl polymer. By the term xe2x80x9cvinyl polymerxe2x80x9d is meant an addition polymer that is the reaction product of ethylenically unsaturated monomers. Particularly preferred vinyl polymers are acrylics. Vinyls, especially acrylics, have the added advantage of good adhesion, non-yellowing, are adjustable for high gloss, and have a wide range of glass transition and minimum film forming temperatures. Polymerization of vinyl monomers in the presence of the polyurethane copolymer causes the two polymers to reside in the same latex particle as an interpenetrating or semi-interpenetrating network particle resulting in improved resistance to water, organic solvents and environmental conditions, improved tensile strength, and modulus of elasticity. The presence of groups such as carboxylic acid groups provide a conduit for processing solutions to permeate the coating at pH greater than 7. Preferably, the acid number is maintained at less than or equal to 40 to ensure that overcoat has good adhesion to the substrate below, even at high pH, and makes the overcoat more water-resistant.
A preferred IPN comprises an interpenetrating polyurethane and vinyl polymer. Such an IPN is also sometimes referred to in the trade as a urethane-vinyl copolymer or hybrid copolymer, even though involving essentially no chemical bonds between the two polymer chains. Such an IPN may be conventionally produced by polymerizing one or more vinyl monomers in the presence of the polyurethane prepolymer or a chain extended polyurethane. It is possible to have more than two polymers or for each of the polymer chains to be branched or linear. Suitably, in such an IPN, the weight ratio of polyurethane component to vinyl component is 1:20 to 20:1. The preferred weight ratio of the polyurethane to the vinyl component is about 4:1 to about 1:4, more preferably about 1:1 to 1:4.
Preferably, the polyurethane has an acid number of greater than or equal to 5, preferably less than or equal to 40, more preferably less than or equal to 30. Acid number is in general determined by titration and is defined as the number of milligrams of potassium hydroxide (KOH) required to neutralize 1 gram of the polymer.
Preparation of an aqueous dispersion of a polyurethane-containing component, when a single copolymer, is well known in the art. In a preferred method of preparation, the first step is the formation of a medium molecular weight isocyanate terminated prepolymer by the reaction of suitable di or polyol with a stoichiometric excess of di or polyisocyanates. The prepolymer is then generally dispersed in water via water-solubilizing/dispersing groups that are introduced either into the prepolymer prior to chain extension, or are introduced as part of the chain extension agent. Therefore, small particle size stable dispersions can frequently be produced without the use of an externally added surfactant. The prepolymer in the aqueous solution is then subjected to chain extension using diamines or diols to form the xe2x80x9cfully reactedxe2x80x9d polyurethane.
When a vinyl polymer is present in the polyurethane-containing component, such urethane-vinyl IPN copolymers may be produced, for example, by polymerizing one or more vinyl monomers in the presence of the polyurethane prepolymer or the chain extended polyurethane. The preferred weight ratio of the chain extended polyurethane to the vinyl monomer being about 4:1 to about 1:4, most preferably about 1:1 to 1:4, as mentioned above.
Polyols useful for the preparation of polyurethane dispersions of the present invention include polyester polyols prepared from one or more diols (e.g. ethylene glycol, butylene glycol, neopentyl glycol, hexane diol or mixtures of any of the above) and one or more dicarboxylic acids or anhydrides (succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, maleic acid and anhydrides of these acids), polylactone diols prepared from lactones such as caprolactone reacted with a diol, polyesteramides containing polyols prepared by inclusion of amino-alcohols such as ethanol amine during the polyesterification process, polyether polyols prepared from for example, ethylene oxide, propylene oxide or tetrahydrofuran, polycarbonate polyols prepared from reacting diols with diaryl carbonates, and hydroxyl terminated polyolefins prepared from ethylenically unsaturated monomers. Combinations of such polyols are also useful. As mentioned below, polysiloxane polyols are also useful in forming a polyurethane. See, for example, U.S. Pat. No. 5,876,9810 to Anderson, hereby incorporated by reference, for such monomers. A polyester polyol is preferred for the present invention.
Polyisocyanates useful for making the prepolymer may be aliphatic, aromatic or araliphatic. Examples of suitable polyisocyanates include one or more of the following: toluene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, ethylethylene diisocyanate, 2,3-dimethylethylene diisocyanate, 1-methyltrimethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-phenylene diisocyanate, 4,4xe2x80x2-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, bis-(4-isocyanatocyclohexyl)-methane, 4,4xe2x80x2-diisocyanatodiphenyl ether, tetramethyl xylene diisocyanate, polymethylene polyphenyl polyisocyanates and the like. Methylene bis(isocyanato cyclohexane) is preferred.
Preferably, a suitable portion of the prepolymer also contains at least one comparatively unreactive pendant carboxylic group, in salt form or preferably neutralized with a suitable basic material to form a salt during or after prepolymer formation or during formation of the dispersion. This helps provide permeability of processing solutions through the overcoat at pHs greater than 7 and dispersibility in water. Suitable compounds that are reactive with the isocyanate groups and have a group capable of forming an anion include, but are not limited to the following: dihydroxypropionic acid, dimethylolpropionic acid, dihydroxysuccinic acid and dihydroxybenzoic acid. Other suitable compounds are the polyhydroxy acids which can be prepared by oxidizing monosaccharides, for example gluconic acid, saccharic acid, mucic acid, glucuronic acid and the like. Such a carboxylic-containing reactant is preferably an xcex1,xcex1-dimethylolalkanoic acid, especially 2,2-dimethylol propionic acid.
Suitable tertiary amines which may be used to neutralize the acid and form anionic groups for water dispersability are trimethylamine, triethylamine, dimethylaniline, diethylaniline, triphenylamine and the like.
Chain extenders suitable for optionally chain extending the prepolymer are, for example, active-hydrogen containing molecules such as polyols, amino alcohols, ammonia, primary or secondary aliphatic, aromatic, alicyclic araliphatic or heterocyclic amines especially diamines. Diamines suitable for chain extension of the pre- polyurethane include ethylenediamine, diaminopropane, hexamethylene diamine, hydrazine, aminoethyl ethanolamine and the like.
In accordance with one embodiment of this invention, a urethane-vinyl IPN may be prepared by polymerizing vinyl addition monomers in the presence of the polyurethane prepolymer or the chain extended polyurethane. The solution of the water-dispersible polyurethane prepolymer in vinyl monomer may be produced by dissolving the prepolymer in one or more vinyl monomers before dispersing the prepolymer in water.
Suitable vinyl monomers in which the prepolymer may be dissolved contain one or more polymerizable ethylenically unsaturated groups. Preferred monomers are liquid under the temperature conditions of prepolymer formation, although the possibility of using solid monomers in conjunction with organic solvents is not excluded.
The vinyl polymers useful for the present invention include those obtained by copolymerizing one or more ethylenically unsaturated monomers including, for example, alkyl esters of acrylic or methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, n-octyl acrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, nonyl acrylate, benzyl methacrylate, the hydroxyalkyl esters of the same acids such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate, the nitrile and amides of the same acids such as acrylonitrile, methacrylonitrile, and methacrylamide, vinyl acetate, vinyl propionate, vinylidene chloride, vinyl chloride, and vinyl aromatic compounds such as styrene, t-butyl styrene and vinyl toluene, dialkyl maleates, dialkyl itaconates, dialkyl methylene-malonates, isoprene, and butadiene. Suitable ethylenically unsaturated monomers containing carboxylic acid groups include acrylic monomers such as acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, fumaric acid, monoalkyl itaconate including monomethyl itaconate, monoethyl itaconate, and monobutyl itaconate, monoalkyl maleate including monomethyl maleate, monoethyl maleate, and monobutyl maleate, citraconic acid, and styrene carboxylic acid. Suitable polyethylenically unsaturated monomers include butadiene, isoprene, allylmethacrylate, diacrylates of alkyl diols such as butanediol diacrylate and hexanediol diacrylate, divinyl benzene and the like.
The prepolymer/vinyl monomer solution may be dispersed in water using techniques well known in the art. Preferably, the solution is added to water with agitation or, alternatively, water may be stirred into the solution. Polymerization of the vinyl monomer or monomers is brought about by free radical initiators at elevated temperatures.
Free radicals of any sort may be used including persulfates (such as ammonium persulfate, potassium persulfate, etc., peroxides (such as hydrogen peroxide, benzoyl peroxide, cumene hydroperoxide, tertiary butyl peroxide, etc.), azo compounds (such as azobiscyanovaleric acid, azoisobutyronitrile, etc.), and redox initiators (such as hydrogen peroxide-iron(II) salt, potassium persulfate-sodium hydrogen sulfate, etc.). Preferable free radical initiators are the ones that partition preferably into the oil phase such as the azo-type initiators. Common chain transfer agents or mixtures thereof known in the art, such as alkyl-mercaptans, can be used to control the polymer molecular weight.
Polymerization may be carried out by various methods. In one method, all of the vinyl monomer (the same or different vinyl monomers or monomer mixtures) is added in order to swell the polyurethane prepolymer. The monomers are then polymerized using an oil soluble free radical initiator after dispersing the mixture in water.
In a second alternative method, some of vinyl monomer may be added to swell the pre-polymer prior to dispersing in water. The rest of the monomer is fed into the system during the polymerization process. Other methods include feeding in all the vinyl monomer during the copolymerization process.
Some examples of polyurethane-containing components used in the practice of this invention that are commercially available include NeoPac(copyright) R-9000, R-9699 and R-9030 from NeoResins (Wilmington, Del.), Sancure(copyright) AU4010 from BF Goodrich (Akron, Ohio), and Flexthane(copyright) 620, 630, 790 and 791 from Air Products. An example of the polyurethane-containing copolymer useful in the practice that is commercially available is the NeoRez(copyright) R9679.
In another embodiment of the invention, the water-dispersible polymer is an essentially hydrophobic, substantially amorphous, thermoplastic polyester polymer in which ionic groups or moieties are present in sufficient number to provide water dispersibility prior to coating. The polyester dispersions provide advantageous properties such as good film-formation, good chemical-resistance, wet-abrasion resistance, excellent fingerprint resistance, toughness, elasticity and durability. Furthermore, the polyesters exhibit tensile and flexural strength and resistance to various oils.
Procedures for the preparation of polyester ionomers are described in U.S. Pat. Nos. 3,018,272; 3,563,942; 3,734,874; 3,779,993; 3,929,489; 4,307,174, 4,395,475, 5,939,355 and 3,929,489, the disclosures of which are incorporated herein by reference. The substantially amorphous polyesters useful in this invention comprise dicarboxylic acid recurring units typically derived from dicarboxylic acids or their functional equivalents and diol recurring units typically derived from diols. Generally, such polyesters are prepared by reacting one or more diols with one or more dicarboxylic acids or their functional equivalents (e.g. anhydrides, diesters or diacid halides), as described in detail in the cited patents. Such diols, dicarboxylic acids and their functional equivalents are sometimes referred to in the art as polymer precursors. It should be noted that, as known in the art, carbonylimino groups can be used as linking groups rather than carbonyloxy groups. This modification is readily achieved by reacting one or more diamines or amino alcohols with one or more dicarboxylic acids or their functional equivalents. Mixtures of diols and diamines can be used if desired.
Conditions for preparing the polyesters useful in this invention are known in the art as described above. The polymer precursors are typically condensed in a ratio of at least 1 mole of diol for each mole of dicarboxylic acid in the presence of a suitable catalyst at a temperature of from about 125xc2x0 to about 300xc2x0 C. Condensation pressure is typically from about 0.1 mm Hg to about one or more atmospheres. Low-molecular weight by-products can be removed during condensation, e.g. by distillation or another suitable technique. The resulting condensation polymer is polycondensed under appropriate conditions to form a polyester. Polycondensation is usually carried out at a temperature of from about 150 to about 300xc2x0 C. and a pressure very near vacuum, although higher pressures can be used.
Polyester ionomers, useful in the present composition, contain at least one ionic moiety, which can also be referred to as an ionic group, functionality, or radical. In a preferred embodiment of the invention, the recurring units containing ionic groups are present in the polyester ionomer in an amount of from about 1 to about 12 mole percent, based on the total moles of recurring units. Such ionic moieties can be provided by either ionic diol recurring units and/or ionic dicarboxylic acid recurring units, but preferably by the latter. Such ionic moieties can be anionic or cationic in nature, but preferably, they are anionic. Exemplary anionic ionic groups include carboxylic acid, sulfonic acid, and disulfonylimino and their salts and others known to a worker of ordinary skill in the art. Sulfonic acid ionic groups, or salts thereof, are preferred.
One type of ionic acid component has the structure
where M=H, Na, K or NH4.
Ionic dicarboxylic acid recurring units can be derived from 5-sodiosulfobenzene-1,3-dicarboxylic acid, 5-sodiosulfocyclohexane- 1,3-dicarboxylic acid, 5-(4-sodiosulfophenoxy)benzene-1,3-dicarboxylic acid, 5-(4-sodiosulfophenoxy)cyclohexane-1,3-dicarboxylic acid, similar compounds and functional equivalents thereof and others described in U.K. Patent Specification No. 1,470,059 (published Apr. 14, 1977). Other suitable polyester ionomers for protective overcoats in the imaged elements of the present invention are disclosed in U.S. Pat. Nos. 4,903,039 and 4,903,040, which are incorporated herein by reference.
Another type of ionic dicarboxylic acid found useful in the practice of this invention are those having units represented by the formula:
wherein each of m and n is 0 or 1 and the sum of m and n is 1; each X is carbonyl; Q has the formula:
Qxe2x80x2 has the formula:
Y is a divalent aromatic radical, such as arylene (e.g. phenylene, naphthalene, xylylene, etc.) or arylidyne (e.g. phenenyl, naphthylidyne, etc.); Z is a monovalent aromatic radical, such as aryl, aralkyl or alkaryl (e.g. phenyl, p-methylphenyl, naphthyl, etc.), or alkyl having from 1 to 12 carbon atoms, such as methyl, ethyl, isopropyl, n-pentyl, neopentyl, 2-chlorohexyl, etc., and preferably from 1 to 6 carbon atoms; and M is a solubilizing cation and preferably a monovalent cation such as an alkali metal or ammonium cation.
The protective overcoat 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), 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 water-dispersible polymers 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 imaging element can be coated applied by several different methods. For example, the polymer overcoats can be coated simultaneously with the gelatin or emulsion containing layers using a slide hopper, and the entire coating was chill-set, dried and wound. However, any of a number of well known techniques can be employed for applying the coatings simultaneously to a substrate comprising the support, such as the use of multi-stations, wherein each station may be able to coat one or more solution. Preferably, a commercial embodiment involves simultaneous co-extrusion or slide hopper coating. Also, on a commercial scale, the coatings are applied to a continuous web, which is later cut into sheets for packaging and sale for individual use by the consumer.
After applying the coated layers to the support, it may be dried over a suitable period of time. The layers are 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.
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). It may be advantageous to increase the amount of polyvinyl alcohol in the overcoat as the laydown increases in order to improve the developability. In the event of cracking, especially at lower levels of polyvinyl alcohol or when using an alternative film-forming polymer, it may be advantageous to adjust the temperature and/or humidity of the drying step to eliminate or reduce this cracking problem.
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 a 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 lattices 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 1xc3x971010 ohms/square, preferably less than 1xc3x97109 ohms/square, and more preferably, less than 1xc3x97108 ohms/square.
Photographic elements 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.
During photoprocessing, the photographic element is preferably 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 and/or other water-soluble polymers, according to one embodiment of the present invention, facilitates the present method. For example, it has been found polyvinyl alcohol polymer 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 a water-soluble polymer in the overcoat is washed out during processing of the exposed photographic element, such that the final product is depleted in water-soluble 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 is illustrated by the following examples. Unless otherwise indicated, the molecular weights herein are weight average molecular weights, as determined by size exclusion chromotagraphy described below.

Method for processing a photographic element comprising a simultaneously coated protective overcoat