Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means

Definitions

• the present invention relates to photographic emulsions on substrates having a subbing or priming layer thereon.
• Typical photographic supports comprise a base material (e.g., polyester, cellulose triacetate, or paper) with a subbing layer on at least one surface to assist in the adherence of the gelatin layers, including the emulsion layers, to the base.
• base material e.g., polyester, cellulose triacetate, or paper
• subbing layer on at least one surface to assist in the adherence of the gelatin layers, including the emulsion layers, to the base.
• Conventional subbing layers are described in U.S. Patent Nos. 3,343,840, 3,495,984, 3,495,985 and 3,788,856.
• the present invention relates to photographic elements having at least one silver halide emulsion layer over a substrate, where the substrate has at least one polymeric surface to which is adhered a layer comprising a gelled or hydrolyzed network of inorganic oxide particles containing an ambifunctional silane.
• the present invention relates to photographic elements. These elements comprise a substrate having at least one silver halide emulsion layer on a surface thereof. A surface with an emulsion thereon is hereinafter referred to as a major surface of the substrate.
• the silver halide emulsion generally comprises silver halide grains (also referred to as crystals or particles) carried in a water-penetrable binder medium of a hydrophilic colloid. It has been recently found that the use of a gelled or hydrolyzed network of inorganic particles, preferably oxides, as a layer on a polymeric surface provides an excellent subbed (or primed) substrate for photographic emulsions (U.S. Patent Application Serial No. 40930, filed April 21, 1987).
• this gelled particulate layer is capable of providing one or more excellent properties to the photographic element including, but not limited to antistatic properties, ease of coatability of the particulate layer, photoinertness (harmless to the photographic emulsion and its properties), adhesion (both wet and dry, to both the substrate and the emulsion layers), and reduction in specular reflectance (i.e., antihalation properties).
• wet adhesion can be weak during development processing. It has been hypothesized that the bond between the gelled network and the gelatin is an acid/base bond. During the elevated pH conditions of development, this bond is sufficiently weakened so that other materials in the emulsion will compete with the gelatin for reaction with sites on the sol-gel coating. This can weaken the bond between the gelatin layer and gelled network layer. Lifting or separation of the layers can result.
• ambifunctional silane means that the compound has reactive silanes on one end of the molecule and a different reactive species capable of reacting with a photographic hardener for gelatin or directly with gelatin.
• This second functionality enables the compound to react with the inorganic particle (through the silane group) and also react with the gelatin (reacting with the gelatin hardener which also reacts with the gelatin).
• the preferred second functional groups on the compound are amino groups and epoxy (e.g., glycidyl) groups.
• the second functionality may be present as a single functional moiety or may be present as a multiple number of such groups.
• a formula that may be used to represent many of the ambifunctional silanes of the present invention is (Q) n -R-Si(OR1)3 wherein R1 is alkyl or aryl, R is an organic group with (n+1) external bonds or valences, n is 1 or 2, and Q is a moiety reactive with photographic hardeners or directly with gelatin (e.g., alpha-amino acids).
• R1 is alkyl of 1 to 10 carbon atoms and most preferably 1 to 4 carbon atoms.
• R is preferably an aliphatic or aromatic bridging group such as alkylene, arylene, alkarylene, or aralkylene which may be interrupted with ether linkages (oxygen or thioethers), nitrogen linkages, or other relatively inert moieties.
• R is alkylene of 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms, with n equal to 1.
• Q is preferably epoxy, or amino, primary or secondary, more preferably primary amino.
• the second functional group may be present as a multiple number of such groups it is meant that the moiety (Q) n -R- may include moieties such as NH2-(CH2)2-NH-(CH2)2-NH-(CH2)3- NH2-(CH2)-3 (NH2)2-CH-CH2- and
• the substrates may comprise any material having at least one polymeric surface which is to be used as the major surface of the substrate.
• the finished emulsion is coated on a suitable support.
• Supports which can be used include films of synthetic polymers such a polyalkyl acrylate or methacrylate, polystyrene, polyvinyl chloride, partial formalation polyvinyl alcohol, polycarbonate, polyesters such as polyethylene terephthalate, and polyamides, films of cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose triacetate, and cellulose acetate butyrate, paper covered with ⁇ -olefin polymers or gelatin (a natural polymer), for example, and synthetic papers made of polystyrene; that is, any of transparent or opaque support commonly used in photographic elements can be used.
• synthetic polymers such as polyalkyl acrylate or methacrylate, polystyrene, polyvinyl chloride, partial formalation polyvinyl alcohol, polycarbonate, polyesters such as polyethylene terephthalate, and polyamides
• films of cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose triacetate
• Primed polymeric substrates are also useful, including, but not limited to, gelatin-primed polymers (e.g., gelatin on poly(ethylene terephthalate)), and poly(vinylidene chloride) copolymers on polyester.
• Other primers such as aziridines, acrylates, and melamine-formaldehyde are also known. This includes polymeric materials loaded with pigments and particulates such as titania to improve the white background of the image and to provide antihalation or other sensitometric effects.
• the substrates may be used with any type of photographic silver halides including, but not limited to silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver bromoiodide and silver chloroiodide grains, which may be in any of the many available crystal forms or habits including, but not limited to cubic, tetrahedral, lamellar, tabular, orthorhombic grains, etc.
• Soluble silver salts and soluble halides can be reacted by methods such as a single jet process, a double jet process, and a combination thereof.
• a procedure can be employed in which silver halide grains are formed under the presence of an excess of silver ions (a so-called reverse mixing process).
• a so-called controlled double jet process can also be employed in which the pAg of the liquid phase wherein the silver halide is formed is kept constant.
• Two or more silver halide emulsions which have been prepared independently may be used in combination with each other.
• Soluble salts are usually removed from the silver halide emulsion after the precipitate formation or physical ripening of the silver halide emulsion.
• a noodle water-washing method can be employed in which the soluble salts are removed by gelling the emulsions.
• a flocculation method utilizing inorganic salts containing polyvalent anions, anionic surface active agents, anionic polymers or gelatin derivatives can also be used.
• the silver halide emulsions are usually chemically sensitized. This chemical sensitization can be carried out, for example, by the methods as described in H. Frieser ed., Die Unen der Photographischen Sawe mit Silverhalogeniden , Akademische Verlagsgesellschaft, pp. 675-734 (1968).
• a sulfur sensitization method using sulfur-containing compounds capable of reacting with active gelatins and silver e.g., thiosulfates, thioureas, mercapto compounds, and rhodanines
• a reduction sensitization method using reducing substances e.g., stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, and silane compounds
• a noble metal sensitization method using noble metal compounds e.g., gold complex salts, and metal complex salts of Group VIII metals, such as platinum, rhodium, iridium, and palladium, of the Periodic Table
• noble metal compounds e.g., gold complex salts, and metal complex salts of Group VIII metals, such as platinum, rhodium, iridium, and palladium, of the Periodic Table
• the sulfur sensitization method is described in detail, for example, in U.S. Patent Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668 and 3,656,955; the reduction sensitization method, in U.S. Patent Nos. 2,983,609, 2,419,974 and 4,054,458; and the noble metal sensitization method, in U.S. Patent Nos. 2,399,083, 2,448,060 and British Patent No. 618,061.
• photographic emulsions which are used in the present invention may be incorporated various compounds for the purpose of, e.g., preventing the formation of fog during the production, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, many compounds known as antifoggants or stabilizers, such as azoles (E.G., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, and mercaptotetrazoles, (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, thioketo compounds (e.g., oxazolinethione), azainden
• the photographic emulsion layers of the light-sensitive material of the present invention may contain polyalkylene oxide or its derivatives (e.g., ethers, esters and amines), thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, hydroquinone or its derivatives for the purpose of increasing sensitivity or contrast, or accelerating development.
• polyalkylene oxide or its derivatives e.g., ethers, esters and amines
• thioether compounds e.g., thiomorpholines
• quaternary ammonium salt compounds e.g., urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, hydroquinone or its derivatives for the purpose of increasing sensitivity or contrast, or accelerating development.
• binders or protective colloids to be used in the emulsion layers and intermediate layer of the light-sensitive material of the present invention it is advantageous to use gelatins.
• other hydrophilic colloids can be used.
• proteins such as gelatin derivatives, graft polymers of gelatin and other polymers, albumin, and casein, sugar derivatives such as cellulose derivatives (e.g., hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate), sodium alginate, and starch derivatives, and various synthetic hydrophilic polymeric substances, homopolymers or copolymers, such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly(N-vinyl)pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, and polyvinyl pyrazole can be used.
• the light-sensitive material of the present invention is particularly effectively used as a black-and-white reflection light-sensitive material which is to be subjected to rapid processing.
• it can be used, e.g. as an X-ray recording light-sensitive material, a photomechanical process light-sensitive material, a light-sensitive material to be used in a facsimile system, and further, as a multilayer, multicolor photographic light-sensitive material having at least two different spectral sensitivities.
• the multilayer, multicolor photographic material usually comprises a support, and at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on the support.
• the order in which the above layers are arranged can be chosen appropriately.
• the red-sensitive emulsion layer contains cyan dye forming couplers
• the green-sensitive emulsion layer contains magenta dye forming couplers
• the blue-sensitive emulsion layer contains yellow dye forming couplers. In some cases, other combinations can be employed. Even in the case of the multilayer, multicolor photographic material, the effects of the present invention are exhibited significantly in a reflection light-sensitive material.
• Spectral sensitizing dyes may be used in one or more silver halide emulsions useful on the subbed substrates used in the present invention. These sensitizing dyes are well known in the art to increase the sensitization of silver halide grains to various portions of the electromagnetic spectrum such as the ultraviolet, blue, green, yellow, orange, red, near infrared, and infrared. These dyes may be used singly or in combination with other dyes to sensitize the emulsions.
• the substrates used in the invention bear a coating comprising a continuous gelled network of inorganic oxide particles, the network containing an ambifunctional silane.
• the particles preferably have an average primary particle size of less than about 50nm (500 ⁇ ), more preferably less than about 20nm (200 ⁇ ).
• continuous refers to covering the surface of the substrate with virtually no straight-line penetrable discontinuities or gaps in the areas where the gelled network is applied. However, the layer may be and usually is porous, without significant straight-line pores or gaps in the layer.
• gelled network refers to an aggregation of colloidal particles linked together to form a porous three-dimensional network.
• the silane will be hydrolyzed at the OR' positions, substituting hydroxy groups for the OR'groups. For example, a triethoxysilane will become a trihydroxysilane.
• the hydrolyzed silane molecules may associate with the inorganic oxide particles by "oxane" bonding in a reversible fashion (SiOH + HOM(particle) ⁇ --> Si-O-M(particle)).
• silane molecules As the solution is dried into a coated layer, it is expected that most of the hydrolyzed silane molecules will become associated with inorganic oxide particles through "oxane" bonding such that they cannot be washed out of the coating by a simple water wash.
• the presence of the silane molecules does not prevent the gelled particle network from gaining cohesive strength, although the time required to gain cohesive strength may be increased.
• the coating should be thicker than a monolayer of particles.
• the coating comprises a thickness equal to or greater than three average particle diameters and more preferably equal to or greater than five particle diameters.
• the articles of the invention comprise a substrate which may be transparent, translucent, or opaque to visible light having at least one polymeric surface, and have formed thereon a coating in the form of a continuous gelled network of inorganic oxide particles with an adhesion promoting effective amount of an ambifunctional silane.
• the coated article When the coating is applied to transparent substrates to achieve increased light transmissivity, the coated article preferably exhibits a total average increase in transmissivity of normal incident light of at least two percent and up to as much as ten percent or more, when compared to an uncoated substrate, depending on the substrate coated, over a range of wavelengths extending at least between 400 to 900 nm.
• An increase in light transmission of two percent or more is generally visually apparent and is sufficient to produce a measurable increase in energy transmissivity when the coated substrate is used.
• An increase in transmissivity is also present at wavelengths into the infrared portion of the spectrum.
• the gelled network is a porous coating having voids between the inorganic oxide particles. If the porosity is too small, the antireflectance may be reduced. If the porosity is too large, the coating is weakened and may have reduced adhesion to the substrate.
• the colloidal solution from which the gelled network is obtained is capable of providing porosity of about 25 to 70 volume percent, preferably about 30 to 60 volume percent when dried. The porosity can be determined by drying a sufficient amount of the colloidal solution to provide a dried product sample of about 50 to 100 mg and analyzing the sample using a "Quantasorb" surface area analyzer available from Quantachrome Corp., Syosett, NY.
• the voids of the porous coating provide a multiplicity of subwavelength interstices between the inorganic particles where the index of refraction abruptly changes from that of air to that of the coating material.
• These subwavelength interstices which are present throughout the coating layer, provide a coating which may have a calculated index of refraction (RI) of from about 1.15 to 1.40, preferably 1.20 to 1.30 depending on the porosity of the coating.
• RI index of refraction
• the average primary particle size of the colloidal inorganic oxide particles is preferably less than about 20nm (200 ⁇ ).
• the average primary particle size of the colloidal inorganic oxide particles is more preferably less than about 7nm (70 ⁇ ). When the average particle size becomes too large, the resulting dried coating surface is less efficient as an antireflection coating.
• the average thickness of the dried coating is preferably from about 30 to 1000nm (300 to 10000 ⁇ ), more preferably 80 to 500nm (800 to 5000 ⁇ ) and most preferably from 90 to 200nm (900 to 2000 ⁇ ).
• Such coatings provide good antistatic properties. When the coating thickness is too great, the coating has reduced adhesion and flexibility and may readily flake off or form powder under mechanical stress.
• Articles such as transparent sheet or film materials may be coated on a single side or on both sides to increase light transmissivity, the greatest increase being achieved by coating both sides.
• the process of coating the layer utilized in the present invention comprises coating a substrate with a solution of colloidal inorganic oxide particles (and preferably the silane at this point), the solution preferably containing at least 0.2 to 15, mor preferably 0.5 to 15 weight percent of the particles, the particles preferably having an average primary particle size less than about 50nm (500 ⁇ ), more preferably less than about 20nm (200 ⁇ ), and most preferably less than about 7nm (70 ⁇ ), and drying the coating at a temperature less than that which degrades the substrate, preferably less than about 200°C, more preferably in the range of 80 to 120°C.
• the coating provides the substrate with an average reduction in specular reflectance of at least two percent over wavelengths of 400 to 900nm.
• Coating may be carried out by standard coating techniques such as bar coating, roll coating, knife coating, curtain coating, rotogravure coating, spraying and dipping.
• the substrate may be treated prior to coating to obtain a uniform coating using techniques such as corona discharge, flame treatment, and electron beam. Generally, no pretreatment is required.
• the ambifunctional silane may be added before, during or after coating. It is preferred to add the silane to the coating mixture before coating. If the silane is added after the "gelled network" has been coated and dried, it should be added from a water-containing solution, so that the silane will be in its hydrolyzed form.
• the colloidal inorganic oxide solution e.g., a hydrosol or organosol
• a moderately low temperature generally less than about 200°C, preferably 80-120°C, to remove the water or organic liquid medium.
• the coating may also be dried at room temperature, provided the drying time is sufficient to permit the coating to dry completely.
• the drying temperature should be less than at which the substrate degrades.
• the resulting coating is hygroscopic in that it is capable of absorbing and/or rehydrating water, for example, in an amount of up to about 15 to 20 weight percent, depending on ambient temperature and humidity conditions.
• the colloidal inorganic oxide solution utilized in the present invention comprises finely divided solid inorganic oxide particles in a liquid.
• solution includes dispersions or suspensions of finely divided particles of ultramicroscopic size in a liquid medium.
• the solutions used in the practice of this invention are clear to milky in appearance.
• Inorganic oxides particularly suitable for use in the present invention are those in which the oxide particles are negatively charged, including tin oxide (SnO2), titania, antimony oxide (Sb2O5), silica, and alumina-coated silica as well as other inorganic oxides of Groups III and IV of the Periodic Table and mixtures thereof. The selection of the inorganic oxide is dependent upon the ultimate balance of properties desired.
• the colloidal coating solution preferably contains about 0.2 to 15 weight percent, more preferably about 0.5 to 8 weight percent, colloidal inorganic metal oxide particles. At particle concentrations about 15 weight percent, the resulting coating may have reduced uniformity in thickness and exhibit reduced adhesion to the substrate surface. Difficulties in obtaining a sufficiently thin coating to achieve increased light transmissivity and reduced reflection may also be encountered at concentrations above about 15 weight percent. At concentrations below 0.2 weight percent, process inefficiencies result due to the large amount of liquid which must be removed and antireflection properties may be reduced.
• the thickness of the applied wet coating solution is dependent on the concentration of inorganic metal oxide particles in the coating solution and the desired thickness of the dried coating.
• the thickness of the wet coating solution is preferably such that the resulting dried coating thickness is from about 80 to 500 nm thick, more preferably about 90 to 200 nm thick.
• the coating solution may also optionally contain a surfactant to improve wettability of the solution on the substrate, but inclusion of an excessive amount of surfactant may reduce the adhesion of the coating to the substrate.
• a surfactant include "Tergitol” TMN-6 (Union Carbide Corp.) and “Triton” X-100 (Rohm and Haas Co.).
• the surfactant can be used in amounts of up to about 0.5 weight percent of the solution.
• the coating solution may optionally contain a very small amount of polymeric binder, particularly a hydrophilic polymer binder, to improve scratch resistance, or to reduce formation of particulate dust during subsequent use of the coated substrate.
• polymeric binder particularly a hydrophilic polymer binder
• Useful polymeric binders include polyvinyl alcohol, polyvinyl acetate, gelatin, polyesters, polyamides, polyvinyl pyrrolidone, copolyesters, copolymers of acrylic acid and/or methacrylic acid, and copolymers of styrene.
• the coating solution can contain up to about 5 or greater weight percent of the polymeric binder based on the weight of the inorganic oxide particles, but useful amounts of polymeric binder are generally in the range of about 0.1 to 5 weight percent to reduce particulate dust. These hinders can reduce some of the beneficial properties (e.g., antistatic properties) of the coatings if used in larger amounts, so that they are not most preferred.
• the ambifunctional silane is generally present as at least 0.1% by weight of the solids content of the gelled particulate layer.
• the ambifunctional silane is present as from 1 to 20% by weight of the solids content of the particulate layer. More preferably the silane is present as 0.2 to 10% by weight of the solids content of the particulate layer.
• Each sample described in the attached table is prepared as follows: The sol as received from the manufacturer is diluted with water to the desired percent solids. Then the specified coupling agent is added to the diluted sol. The amount of coupling agent is calculated according to the percent weight to oxide solids. After addition of coupling agent the mixture is vigorously shaken for 30 s to dissolve the coupling agent. Then, 0.05-.1% wt. of Triton X-100 surfactant is added as a coating aid.
• This mixture is coated onto an appropriate substrate film by: 1) a 10 cm x 20 cm sheet of film is placed on a flat surface; 2) a bead of the mixture is drawn across the top of the sheet (about 1 milliliter); 3) the mixture is spread across the sheet by means of a #4 stainless steel wire-wound rod; 4) the coated sheet is dried in an oven for about two minutes at 100°C. The dried coated sheets are allowed to stand at room temperature for one day or more before further use.
• a standard x-ray photographic emulsion is prepared and coated onto the above sheets by: 1) the temperature of the emulsion mixture is adjusted to about 40°C; 2) a bead of the emulsion (approx. 2 ml) is drawn across the top of a sol-coated sheet; 3) the emulsion is spread across the sheet by means of a #24 stainless steel wire-wound rod; 4) the emulsion coated sheet is dried at 50°C for about two hours.
• each sample is given a grade between zero (0) and 10, according to the approximate percentage of emulsion remaining on the sample. Thus if 50% of the emulsion remains the grade is "5". If all of the emulsion remains, the grade is "10".
• the test method is: 1) a 5 cm x 10 cm portion of the x-ray emulsion coated material from above is immersed in x-ray developer at room temperature for two minutes; 2) the material is removed from the developer and, while still wet with developer, scribed in a cross-hatch pattern with the corner of a razor blade, and rubbed with firm pressure in a circular motion for 24 cycles with a rubber glove-tipped index finger; 3) the sample is washed in cold water and dried; 4) a 2.5 cm x 5 cm portion of 3M #610 tape is affixed over the cross-hatched area of the test material and pulled off with a vigorous snap; 5) the sample is graded as described above for emulsion adhesion,
• the substrate film used in the examples was 100 ⁇ m (4-mil) PET primed with about 0.04 ⁇ m (microns) of a poly(vinylidene chloride)-containing terpolymer.
• GPS is ⁇ -glycidoxypropyltrimethoxysilane.
• a silica-coated sample was prepared using the coating mixture 2B and the above-described preparative method. This sample was dipped into a solution of 0.10% APS in ethanol for 15 seconds and air dried. This was then emulsion coated and tested according to the above procedures. The adhesion test result was "10".
• silica-coated samples were prepared using the coating mixture 2B and the above-described preparative method. These samples were coated with x-ray emulsion modified as follows:
• a silica-coated sample was prepared using the coating mixture 1C, except that 0.56g of K&K #1312 gelatin was dissolved in the mixture. This was emulsion coated and tested according to the above procedures. The adhesion test result was "10". Furthermore the conductive and optical properties of the silica-coated sample were comparable to those of silica-coated sample prepared with mixture 1C.
• sol-gel and gelation as they apply to the use of inorganic dispersions of particles in the formation of layers, are well understood in the art. Sol-gels, as previously described, comprise a rigidized dispersion of a colloid in a liquid, that is the gelled network previously described. Gelation is the process of rigidizing the sol-gel.
• the liquid extracted sol-gel coating (which will generally retain some significant amounts of liquid, e.g., at least 0.1% by weight up to 10% or 15% or more by weight in some cases) can be described in a number of various physical terms which distinguish it from other particulate constructions such as sintered, adhesively bound, or thermally fused particles.
• the association of the particles in a sol-gel system is a continuous sol-gel network which is known to mean in the art that the particles form an inorganic polymer network at the intersection of the particle (e.g., as with silica sol-gels), or an inorganic salt system. Bonding forces such as van der Waals forces and hydrogen bonding can form an important part of the mechanism of particle association.
• These characterizations of sol-gel compositions are quite distinct from the use of polymer binders which form a binding medium to keep particles associated and where the particles themselves do not exert direct bonding forces on one another.
• the size of the colloid particles in the sol-gel is important. Processes where particulates are ball-milled generally produce particles of no less than about 1 ⁇ m (micron). Unless a chemical process is used to form the particles of smaller size, which agglomerate to effectively form large particles which are then ball-milled to break up the agglomeration, the particle size limit of about 1 ⁇ m (micron) from physical processing tends to hold true.

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• 1988
  • 1988-07-12 AU AU18957/88A patent/AU603908B2/en not_active Expired
  • 1988-07-20 MX MX1234688A patent/MX12346A/es unknown
  • 1988-07-27 CA CA000573120A patent/CA1338180C/en not_active Expired - Fee Related
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