The invention relates to a photographic element comprising a base and hydrophillic colloid layers comprising at least one layer comprising photosensitive silver halide, wherein said hydrophilic colloid imaging layers further comprise a flexibilizer agent and said flexibilizer agent has a logP of greater than xe2x88x921.2.

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 xcexcm. Dry toners used in xerography are typically 8-10 xcexcm 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 xe2x80x9cmagnetographyxe2x80x9d 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 xe2x88x921.2 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 xe2x88x921.2 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 xe2x88x921.2 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  less than 10xe2x88x924 to  greater than 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 175xc2x0 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 1xc3x971010 ohms/square, preferably less than 1xc3x97109 ohms/square, and more preferably, less than 1xc3x97108 ohms/square.
The terms as used herein, xe2x80x9ctopxe2x80x9d, xe2x80x9cupperxe2x80x9d, xe2x80x9cemulsion sidexe2x80x9d, and xe2x80x9cfacexe2x80x9d 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 xe2x80x9cface stockxe2x80x9d, xe2x80x9csubstratexe2x80x9d and xe2x80x9cbasexe2x80x9d mean the material to which the hydrophilic imaging layers such as silver halide layers are applied. The terms xe2x80x9cbottomxe2x80x9d, xe2x80x9clower sidexe2x80x9d, and xe2x80x9cbackxe2x80x9d 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:
COF=xcexc=(friction force/normal force)
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 xe2x80x9cno label lookxe2x80x9d 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. xe2x80x9cVoidxe2x80x9d is used herein to mean devoid of added solid and liquid matter, although it is likely the xe2x80x9cvoidsxe2x80x9d contain gas. The void-initiating particles which remain in the finished packaging sheet core should be from 0.1 to 10 xcexcm 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 xcexcm. 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 xcexcm 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 Arxe2x80x94C(R)xe2x95x90CH2, 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 CH2xe2x95x90C(Rxe2x80x2)xe2x80x94C(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 Rxe2x80x2 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 CH2xe2x95x90CH(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 xcexcm and 1.5 xcexcm, preferably between 0.5 and 1.0 xcexcm. Below 0.5 xcexcm any inherent nonplanarity in the coextruded skin layer may result in unacceptable color variation. At skin thickness greater than 1.0 xcexcm, there is a reduction in the photographic optical properties such as image resolution. At thickness greater than 1.0 xcexcm, 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 320xc2x0 C. are preferred, as temperatures greater than 320xc2x0 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 xcexcm 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.

Photographic member with flexibilizer material


A dielectric coating for a circuit board which is adherent to electroless copper. The coating is an epoxy dielectric including an amount of a solubilized nitrile-free butadiene or isoprene agent for promoting adhesion of an electroless copper coating. A method for producing a circuit board is also disclosed.

The present invention relates to dielectric coatings for circuit boards which provide adequate adhesion of copper plate. More particularly, the present invention relates to dielectric materials blended with polybutadiene or polyisoprene which are useful in microvia high density printed circuit boards.
Over the years with changes in sophistication of electrical equipment, manufacturers of printed circuit boards have increasingly been forced into producing high density circuits into smaller packages. In some of the most recent advances, high interconnect density on printed circuit boards is provided by utilizing multi-layer circuits which are separated by a dielectric material. These circuits are interconnected by a high density of holes or vias in the dielectric forming pads, sometimes as much as 100-200 pads per square inch. The formation of such pads may be accomplished by coating an existing circuit board surface having copper leads with a thin layer of dielectric material (i.e., 1-3 thousandths of an inch thick). Thereafter, holes (vias) are drilled with a laser or the like through the dielectric to the copper leads. In order to form a second circuit layer and/or via pads, an electroless copper deposition process is used to coat the dielectric material. This also enters the vias and attaches to the underlying copper leads. Thereafter, an electroplated copper is deposited onto the electroless copper and the printed circuit board can be imaged and etched to provide a new circuit board layer.
These vias may also be produced using photo imaging dielectrics. In this process, rather than drilling holes for via pads with a laser, the holes are imaged in the photo imageable dielectric and developed leaving the vias for forming via pads. Again, electroless copper is plated, followed by electroplated copper, which may be etched to form a circuit if desired. Photoimageable microvia technology is discussed in the article entitled xe2x80x9cPhoto Defined Vias Enable High Density Designxe2x80x9d, McDermott, Electronic Packaging and Production, May 1996, p. 45.
While such processes are known, the present dielectric resins used have been found less than adequate for providing adhesion between the electroless copper plates and the dielectric material which is necessary in these microvia applications. Typical known dielectrics are thermoset epoxies when laser drilling of vias is used. Photo imageable dielectrics may be a combination of thermosettable epoxy and photo setting epoxy acrylates.
Electroless plating onto plastic materials has been known in the art for many years. A typical process includes oxidizing of acrylonitrile butadiene styrene (ABS) plastic moldings. This is typically accomplished in a moderately hot chrome sulfuric acid solution. Typically, the polymers used in the ABS blend are acrylonitrile-butadiene-styrene, styrene-butadiene-rubber blended with acrylonitrile-styrene plastic. It is believed that the oxidant attacks the carbon-carbon double bond of the styrene butadiene based rubber to roughen the surface, which allows the electroless copper to adhere to the surface. The acrylonitrile copolymers are very polar. As stated above, circuit board dielectrics are generally either epoxy compositions or epoxy acrylate based compositions which are of relatively low polarity. In attempts to make these epoxy dielectric resins platable with electroless copper, it has been taught that nitrile rubbers were used in order to render these dielectric materials platable.
An example of the use of the nitrile rubber and its incompatibility with the dielectrics used in the printed circuits applications is U.S. Pat. No. 4,628,022, wherein dicarboxy terminated acrylonitrile-butadiene copolymers (nitrile rubbers) are reacted with epoxy and acrylic acid in order to make this polar material compatible with the low polarity epoxy and acrylic resins used as dielectric materials for printed circuit boards. Such reaction products mixed in the formula make the blend platable after oxidative treatment in a conventional 3-step permanganate process.
U.S. Pat. No. 5,545,510, issued Aug. 13, 1996 to Kukanskis (Mac Dermid, Inc.), discloses compositions containing at least one elastomer selected from the group consisting of copolymers of butadiene with acrylonitrile, carboxy terminated butadiene acrylonitrile and epoxy terminated butadiene acrylonitrile copolymers. The adhesion values reported are 0.5, 3.0 and 4.8 lbs/inch.
Nitrile rubbers separate in phases and were found to be incompatible. Therefore, it has been desirable in the art to provide an improved dielectric material which has superior adhesion properties but which is usable within regularly known epoxy dielectric compositions. These dielectric compositions preferably may be cured to a hard consistency and have a high glass transition temperature, low dielectric constant and low dissipation factor. Additionally, it is preferable to provide a dielectric material which is highly adherent to electroless copper in conventional oxidative processes which provides good adhesion of the plated metal.
In accordance with the present invention, there is provided a dielectric coating for a circuit board for providing good adherent characteristics for electroless copper. The dielectric coating comprises an aqueous developing epoxy composition, including an amount of butadiene or isoprene modifying agent effective for promoting adhesion of an electroless copper coating. The additives of the present invention must be soluble in the particular epoxy dielectric material utilized. Thus, because of the negative effect of high polarity compositions such as nitrites, this composition is a nitrile-free butadiene or isoprene-type composition.
Further understanding of the present invention will be had by reference to the detailed description of the preferred embodiments set forth below when taken in conjunction with the examples and claims appended hereto.
In accordance with the present invention, there is provided a dielectric coating for a circuit board for providing good adherent characteristics for electroless copper. In its broad aspects, the present invention comprises an epoxy dielectric composition including an amount of a nitrile-free butadiene or isoprene agent. This agent is effective for promoting adhesion of an electroless copper coating. The butadiene or isoprene agent is solubilized in the epoxy dielectric. In accordance with the method aspects of the present invention, a method of producing a multi-layered printed circuit board is provided, which comprises the steps of first providing a circuit board substrate which includes a surface which has circuitry printed thereon. Next, the surface of the board is coated with an effective amount of a solution of a dielectric material comprising an epoxy resin, and an effective amount of a butadiene or isoprene polymer adhesion promoter. Thereafter, the coating is freed from solvent by heating and baking, and textured by permanganate oxidation, and an electroless copper layer is plated onto the coating, followed by electroplated copper.
The board is then imaged by dry film imaging, primary image and unwanted copper is removed to leave vias and circuits. The dielectric material typically includes epoxy resin-type dielectrics, which are known in the art, with a mixture of from about 2% to about 15%, and preferably 4% to 8% of an adhesion promoter. Typically, such epoxy dielectrics include epoxy resins, epoxy curing agents, rheological additives and mineral fillers. These dielectrics are typically applied in 60-85% by weight solutions in glycol ethers or similar solvents. The nitrile-free butadiene or isoprene polymer adhesion promoters are critical to the present invention. These adhesion promoters, without nitrile groups in the molecule, are polarity compatible with the relatively nonpolar epoxy compositions. Thus, they are soluble in the same types of systems as the epoxies. Thus, the absence of nitrile groups is essential to the present invention in order to provide proper solubility in dielectric compositions of the present invention.
Suitable thermoset epoxy systems used with the present invention are those commonly known in the art. These include epoxy type resins as follows: epoxy novolacs, like Araldite EPN-1138, -1139, cresol novolacs, like Araldite ECN-1235, -1237, -1299, tris-phenol epoxy type, like Tactix-742, -740, 2,3-epoxypropyl isocyanurate, etc., all from Ciba, Specialty Chemicals Corporation.
Suitable epoxy curing agents include the following: melamine (1,3,5-triamino-S-triazine), DICY (dicyan diamide), etc., epoxy curing agent modifiers, like Aneamine 2441, a modified polyamine proprietary from Air Products, imidazoles, like 2-mercaptobenzimidazole, ethyl methyl imidazole, etc.
Typically, such compositions include rheological additives such as the following: polydimethylsiloxanes, such as TSA-750; surfactants, such as Fluorad FC-430 (3 M Co); polyacrylates, such as Modaflow (Monsato); and mixtures of these.
Also, mineral fillers may be utilized as desired. Suitable mineral fillers include the following: fumed silicas, like aerosil 380, 200, R-974 (Degussa), hydrated alumina, mined silicas, like Imisil A-8, barium sulfate and clays such as Benton SD-2.
The nitrile-free butadiene or isoprene polymer adhesion promoters of the present invention may be provided by liquid polybutadienes or may also be provided in epoxy agents which are modified with polybutadienes or polyisoprenes.
The nitrile free diene polymers of the present invention are selected from the group consisting of polybutadiene, polyisoprene epoxidized polybutadiene, epoxidized polyisoprene, carboxy terminated polybutadiene or polyisoprene, carboxy terminated epoxidized polybutadiene, carboxy terminated epoxidized polyisoprene, hydroxy functionalized polybutadiene, hydroxy functionalized polyisoprene, hydroxy functionalized epoxidized polybutadiene, and hydroxy functionalized epoxidized polyisoprene. Examples of suitable adhesion promoters of the present invention include: those obtainable from Aldrich Catalog No. 38,767-3; 41,891-9; 40,620-1, 38,766-5; 38,768-1. Other suitable adhesion agents include EPOLEAD BP3600 and BP4700 obtainable from Dicel of Japan.
Thus, these materials typically are low molecular weight liquid polybutadienes in their free forms or structurally modified forms which are modified for acquiring functional groups. These materials may include polybutadiene epoxy/hydroxy functionalized or polybutadiene hydroxy functionalized or dicarboxy terminated polybutadienes. Such materials typically have a weight average molecular weight of from about 1,000 to about 10,000, with preferable weight average molecular weights including from about 1,000 to about 5,000. Suitable materials for use in the present invention may be manufactured at low cost by anionic polymerization of butadiene monomers which are catalyzed by organolithium compounds. This polymerization yields living polymers which have a molecular weight determined by the ratio of the monomer to the catalyst. These polymers may thereafter be terminated with water to form free polybutadienes or can be terminated with carbon dioxide to form carboxylic acids. Other forms might be terminated with formaldehyde or ethylene oxide to form hydroxy terminated polymers. If the material is reacted with epichlorohydrine, epoxy terminated monomers may be formed. Alternatively, reacting with organic peroxides can form epoxy groups on the backbone of the polydienes. Polyisoprene can be subjected to the same chemical processes and used as adhesion promoters in the present invention. While low molecular weight polybutadienes are typically liquid and soluble in the epoxy dielectric systems, other higher molecular weight polybutadienes and polyisoprenes may be used, provided they are soluble in a suitable solvent which is compatible with the dielectric solvent system. Typically, glycol ethers will provide suitable solubility in compounds of the present invention.
In accordance with the process aspects of the present invention, a multi-layered circuit board is produced as follows. First, a suitable printed circuit board is provided which includes a surface thereof having circuitry printed thereon. Manufacture of printed circuit boards and the like is known in the art. Additionally, the etching and formation of circuitry on such boards of copper plate is also known in the art. After the circuit has been formed on the board, the dielectric material described above is coated onto the printed circuit board. In a preferred aspect of the present invention, high interconnect density printed circuit boards are produced by providing a coating of 1-3 thousandths of an inch thick and drilling holes as much as 100-200 per square inch in the board where necessary for connection to the circuitry. Thereafter, the board is treated with an oxidizing process to texture the surface for subsequent plating of electroless copper. Oxidizing processes are known in the art and generally comprise the following. First, an aqueous solution of neutral or alkaline solvents is used to swell the dielectric material. Then an aqueous solution of potassium or sodium permanganate and sodium hydroxide is used, followed by an aqueous solution of a reducer such as hydrazine, hydroxylamine, sulfuric hydrogen peroxide or the like.
A typical process used in electroless copper plating is as follows. First, the dielectric surface is prepared prior to plating with first a cleaner or conditioner based aqueous surfactant, preferably an alkanolamine such as ethanolamine. A copper etchant solution is used to etch the surface. This etchant may be based on acidic peroxysulfates or persulfate solutions as are known in the art. A palladium based activator is then used and then a postactivator. Thereafter, electroless copper is plated onto the treated dielectric using a suitable process such as Enplate Cu-406, available from Enthone-OMI, Inc., West Haven, Conn.
Thereafter, an electroplated copper layer is plated onto the electroless copper. Electroplating copper solutions are known in the art. Any suitable acid copper electroplate may be used, such as XR-235, obtainable from Enthone-OMI, Inc. of West Haven, Conn.
Thereafter, the new layer of electroplated copper may be imaged and etched as is known to those skilled in the art. In the present invention, adhesion of the electroless copper layer to the dielectric coating is critical to providing high quality printed circuit boards. Adhesion in excess of 6 pounds per inch is obtainable under controlled process conditions of the present invention.

Platable dielectric materials for microvia technology


A two-piece panel fastener includes a barrel-shaped metal retainer which holds a screw. The screw includes a threaded shaft and a plastic cap which has longitudinally-extending resilient fingers which engage the outer surface of the retainer to captivate the screw. The retainer has a chamfered top flange along its top edge, a circumferential bulge area around its outer surface approximately in the middle of its length, and a base at the bottom. Two circumferential valley regions of reduced diameter are located along the outer surface of the retainer. The first valley region is located between the chamfered top flange and the bulge area and the second is located between the bulge area and the base. When the fingers occupy either of the valley regions, the screw is captively held at either of two stable positions of retraction or extension. The retainer is preferably rigidly affixed to a circuit board by soldering a base flange at the bottom of the retainer to the top surface of the board. After the retainer is separately soldered to the circuit board and the retainer has cooled, the screw and cap assembly are joined to the retainer by snap action of the resilient cap fingers.

The present invention relates to panel fasteners affixed to circuit boards and, in particular, to panel fasteners of the type having a molded cap composed of a material such as ABS Plastic. More specifically, it relates to panel fasteners of the type disclosed in U.S. patent application Ser. No. 09/739,689 entitled xe2x80x9cSnap-In Panel Fastenerxe2x80x9d which is herein incorporated by reference as though fully set forth.
There are cases in which panel fasteners of the hybrid type, that is fasteners in which the screw portion has a molded-on plastic cap for ease of manual operation, are required to be soldered to a printed circuit board. A problem arises, however, due to the soldering temperature required to affix the retainer portion of the panel fastener to the PCB because the soldering heat has an adverse effect on the materials used in the plastic portion of the panel fastener. This problem not only arises with regard to soldering to PCBs but may also arise in other situations where attachment of the retainer to a base panel requires elevated temperatures. There is therefore a need in the art to provide a hybrid-type panel fastener that may be soldered or applied to a base panel by heating without adversely affecting its plastic portion.
In order to meet this need in the art, the present invention has been devised in which the two main components of the panel fastener, the screw cap portion and the metal retainer portion, are assembled together after the retainer is soldered to the PCB and the retainer has cooled. The screw cap assembly is later attached to the soldered retainer by the snap action of its resilient parts. Since the screw cap is away from the heat during soldering the retainer, it cannot be adversely affected. Accordingly, the present invention provides a unique snap-together method provided by its structure which permits a low insertion force that can be accomplished by hand as well as automatic equipment so that the fastener can easily be installed onto a retainer after it has been soldered to a circuit board without damage to the PCB. Since the high force of assembly required by prior art hybrid-type panel fasteners would severely damage the PCB and also require expensive installation equipment and tooling, the low assembly force of the screw cap assembly to the retainer of the invention avoids these problems.
More specifically, the applicants have invented a two-piece panel fastener comprising a generally barrel-shaped metal retainer which holds a screw. The retainer has a chamfered top flange along its top edge, a circumferential bulge area along its outer surface approximately in the middle of its length, and a base at the bottom. Two circumferential valley regions of reduced diameter are located along the outer surface of the retainer. The first valley region is located between the chamfered top flange and the bulge area and the second is located between the bulge area and the base. The screw includes a threaded shaft and a plastic cap which has longitudinally-extending resilient fingers as means to engage the outer surface of the retainer to captivate the screw. The screw is captively held at either of two stable positions of retraction or extension where the fingers occupy either of the valley regions. The retainer is preferably rigidly affixed to a circuit board by soldering a base flange at the bottom of the retainer to the top surface of the panel. The shank extends axially downward from the flange and lies within a hole in the PCB during soldering. The threaded portion of the screw extends beyond the shank of the retainer when the screw is in the extended position.
The method of assembling the captive panel fastener to a printed circuit board comprises the steps of placing an axially-extending shank of a captive fastener retainer through a mounting hole in a printed circuit board, soldering the retainer to the printed circuit board, cooling the retainer, and then affixing a retractable screw assembly including a plastic screw cap to the retainer by snap attachment of the screw cap to an outside surface of the retainer.
In another embodiment, the panel fastener comprises a generally cylindrical retainer having a base flange at the bottom. An inward-facing flange is located at the top of a through-hole in the retainer, and includes a lead-in ramp at the top and a steep angle on an underside. The screw has a threaded shaft and a plastic cap rigidly affixed to its head. A deformable ring is located around the shaft of the screw at the top of a threaded region and has a relaxed diameter greater than the inside diameter of the retainer through-hole flange such that the ring engages an underside of the flange when the screw is retracted thereby captivating the screw.
The applicants have therefore devised a unique two-piece hybrid panel fastener with a structure and method of attachment which permits it to be used in solder-on applications to PCBs without damage to either the fastener or the PCB. Other objects and advantages of the present invention will become apparent to those of skill in the art from the following drawings and description of the preferred embodiment.