EP0831363A1 - Crystaux d'émulsion sensibilisés à l'halogénure d'argent avec de la silice colloidale en tant que seule colloide protecteur pendant la précipitation - Google Patents

Crystaux d'émulsion sensibilisés à l'halogénure d'argent avec de la silice colloidale en tant que seule colloide protecteur pendant la précipitation Download PDF

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Publication number
EP0831363A1
EP0831363A1 EP96202612A EP96202612A EP0831363A1 EP 0831363 A1 EP0831363 A1 EP 0831363A1 EP 96202612 A EP96202612 A EP 96202612A EP 96202612 A EP96202612 A EP 96202612A EP 0831363 A1 EP0831363 A1 EP 0831363A1
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EP
European Patent Office
Prior art keywords
silver halide
silver
selenium
gold
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96202612A
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German (de)
English (en)
Inventor
Peter c/o Agfa-Gevaert N.V. Verrept
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Agfa Gevaert NV
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Agfa Gevaert NV
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Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP96202612A priority Critical patent/EP0831363A1/fr
Priority to JP27051097A priority patent/JPH10104770A/ja
Publication of EP0831363A1 publication Critical patent/EP0831363A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances

Definitions

  • This invention relates to a method of preparing light-sensitive emulsions having sensitised silver halide crystals with colloidal silica as a protective colloid and to materials coated with layers containing the said emulsions.
  • Highly light-sensitive silver halide crystals having a cubic or a tabular habit are known to be very sensitive to pressure sensitisation, a phenomenon which is known as "pressure sensitivity" which may appear as pressure marks, pressure sensitisation or desensitisation, wherein both the protective colloid and the coated matrix have to dissipate the energy developed by the pressure force when the coated layer is dried and deformed afterwards in packaging, before and after exposure and by processing. In the dry state pressure sensitisation or desensitisation may occur.
  • emulsions having regular or tabular grains are further made ready for coating by addition to the emulsion of an amount of hydrogen-bridge forming polymer and/or silica in such an amount that the ratio of hydrogen bridge-forming polymer to silver halide expressed as silver nitrate is comprised between 0.05 and 0.40 and the ratio of silica to silver halide expressed as silver nitrate is comprised between 0.03 and 0.30.
  • Gelatin is well-known as the most commonly used protective colloid. It has the characteristics of a thermoreversible polymer, showing a sufficient gel strength after coating, but more important is its stabilising function of silver halide nuclei, growing silver halide crystals and although adsorbed to the said crystals permitting chemical ripening and spectral sensitisation without having restraining properties thereupon.
  • colloidal silica sol as a sole protective colloid during precipitation however in order to get the required sensitometric characteristics, especially high speed, suitable gradation and low fog, it is of utmost importance to create optimal chemical and spectral sensitisation circumstances, taking into account the preferred ratios of colloidal silica to onium compound (used as a co-stabiliser) and colloidal silica to silver coated mentioned hereinbefore in both published EP-Applications.
  • Suitable examples of the said phosphonium compounds are disclosed in US-A 3,017,270.
  • suitable examples are mentioned of cationic polyalkylene oxide salts including e.g. quaternary ammonium and phosphonium and bis-quaternary salts.
  • Onium salt polymers wherein the onium group may be e.g. a phosphonium group, are disclosed in US-A 4,525,446.
  • Other onium compounds as e.g. sulphonium compounds as disclosed in e.g. in EP-Specification 0 392 092 may also be used in minor amounts in combination with the preferred phosphonium compounds, used in the method of preparing emulsions according to this invention.
  • a preferred co-stabilising phosphonium compound used in the method according to the present invention is (Phen) 3 -P + -CH 2 -CH 2 OH.Cl - , wherein Phen represents phenyl as has been described e.g. in EP-A 0 677 773.
  • Phen represents phenyl as has been described e.g. in EP-A 0 677 773.
  • This feature is illustrative for the protective action of the silica sol in the presence of an onium compound, thereby acting as a "network-stabilising" agent.
  • the said phosphonium compound therein is moreover controlling and (co-)stabilising the preferred crystal habit of the regular (cubic or octahedral) or tabular ( ⁇ 111 ⁇ or ⁇ 100 ⁇ ) silver halide crystals during nucleation and crystal growth in the silver halide precipitation step of the method according to this invention.
  • a composition of the said silver halide crystals any combination of chloride, bromide and iodide is possible.
  • silver halide emulsion crystals are chemically ripened in the presence of an onium precursor compound together with a combination of compounds generating sensitisation specks comprising silver, gold and selenium or silver, gold, selenium and sulphur.
  • the preferred onium compound and the said onium precursor compound are both phosphonium compounds.
  • the light-sensitive silver halide emulsion prepared in accordance with the method of the present invention is thus present as a so-called primitive emulsion as long as no sulphur, selenium or gold compounds or selenium and gold are added to the reaction vessel.
  • chemical sensitisation proceeds with a combination of gold and selenium or gold, selenium and sulphur.
  • Selenium compounds which, apart from onium precursor compounds, are generating selenium as disclosed hereinbefore, can be used during chemical ripening and have e.g. been described in US-P 5,112,733 wherein chemical sensitisation is further performed in the presence of a palladium compound.
  • thick tabular grain emulsions having an average aspect ratio from 3 to 8 and ten or more dislocation lines per grain are e.g. chemically sensitised with at least one selenium sensitiser, at least one gold sensitiser and at least one sulphur sensitiser.
  • tellurium compounds may partially replace selenium compounds.
  • Preferred amounts of said sulphur, selenium and gold compounds added during the chemical ripening step are depending on the crystal size (crystal surface available) of the emulsion crystals, but, according to this invention in order to get a preferred fog-sensitivity relationship, the formation of sensitisation specks comprising silver, gold and selenium or silver, gold, selenium and sulphur during the step of chemically ripening the said silver halide requires
  • the said molar ratios are illustrative for the fact that higher amounts of selenium are needed, unless higher amounts of gold are present in order to suppress fog as will be illustrated in the Examples hereinafter.
  • the emulsions sensitised by means of gold-sulphur-selenium or gold-selenium ripeners as in the present invention can be treated before chemical sensitisation with reductors as e.g. tin compounds as has been described in GB-A 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • reductors as e.g. tin compounds as has been described in GB-A 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • Chemical sensitisation can also be performed in the presence of small amounts of Ir, Rh, Ru, Pb, Cd, Hg, Tl, Pd, Pt, or Au.
  • One of these chemical sensitisation methods or a combination thereof can be used.
  • a mixture can also be made of two or more separately precipitated emulsions being chemically sensitised before mixing them.
  • desalting of the reaction medium proceeds before, during and/or after chemically ripening the said silver halide, whereas redispersing of the silver halide proceeds before, during or after chemically ripening the said silver halide.
  • Said desalting may proceed by flocculation as has been described e.g. in EP-A's 0 517 961 and 0 704 749 or by ultrafiltration.
  • the step of spectrally sensitising the silver halide crystals is further included, wherein chemical ripening is performed before, during and/or after the said step. It has been found that in a preferred embodiment chemical sensitisation is performed after addition of the spectral sensitiser(s), which can be added integrally, in portions or consecutive. Said addition of spectral sensitiser may be performed already during the precipitation step.
  • onium precursor compounds according to the formula (III) are added during precipitation of silver halide regular or tabular grains the onium precursor compound, depending on its structure, decomposes as a function of time after being added to the reaction vessel and generates selenium which acts as a ripening agent during precipitation of silver halide crystals, further reacting to form a chemical sensitisation speck together with silver and gold or silver, gold and sulphur.
  • colloidal silica is used as a sole protective colloid during precipitation, no disadvantage as observed after precipitation in gelatinous medium wherein part of the gold compounds forms complexes with the gelatinous binder, thereby reducing its ripening activity and causing instability during preservation.
  • sensitisation specks composed of silver, gold and selenium or silver, gold, selenium and sulphur are generated at whatever a moment during and/or after precipitation of silver halide, it is possible to controll the internal and surface sensitivity of the silver halide crystals prepared according to the method of this invention.
  • Any combination of silver with gold and/or sulphur and/or selenium as chemical sensitisation speck can be generated in the method of this invention and compositions of the said specks will depend on amounts of chemical compounds added, on chemical ripening time, on chemical ripening temperature in the reaction medium wherein said chemical ripening proceeds and on conditions of pAg, determining the amount of silver ions present in the reaction medium.
  • Spectral sensitisation of the light-sensitive silver halide crystals can be performed with methine dyes such as those described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons.
  • Dyes that can be used for the purpose of spectral sensitisation include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes, complex merocyanine dyes.
  • Suitable supersensitisers are i.a. heterocyclic mercapto compounds containing at least one electronegative substituent as described e.g. in US-A 3,457,078, nitrogen-containing heterocyclic ring-substituted aminostilbene compounds as described e.g. in US-A 2,933,390 and US-A 3,635,721, aromatic organic acid/formaldehyde condensation products as described e.g. in US-A 3,743,510, cadmium salts, and azaindene compounds.
  • the preferred cubic and tabular silver halide emulsion crystals according to this invention are spectrally sensitised with at least one dye having a structure corresponding to the general formula (IV) given below, wherein
  • Preferred spectral sensitisers suitable for use together with the emulsion crystals used in the method according to this invention are those of the type where R''' is -C 2 H 5 , Z is an oxygen atom, and where at least one of R and R' represents
  • Another class of preferred spectral sensitisers suitable for use together with the emulsion crystals according to this invention are those of the type where R''' is hydrogen, Z is an nitrogen atom; wherein T represents 5-phenyl, 5-Cl, 5-OCH 3 or 5-CH 3 and wherein T' represents 5,6-(Cl) 2 ; 5-CN-6-Cl; 5-CF 3 -6-Cl; 5-Cl; 5-CN, 5-CF 3 , 5-CHF 2 , 5-SO 2 CH 3 , 5-SO 2 R''''' (R''''' representing a fluoro-subsituted or non-fluoro-substituted alkylgroup), 5-COOR'''''' and 5-SO 2 -N(R x )(R y ) or 5-CO-N(R x )(R y ), wherein R x and R y may each independently represent substituted or unsubstited alkyl groups, or which may each independently or together form a ring with the
  • Especially preferred structures of the type wherein Z represents oxygen are those wherein T and T' each represent Cl or T represents Cl and T' represents Phenyl or vice versa and wherein R and R' each independantly represent one of the combinations of the formulae
  • An especially preferred spectral sensitiser according to the general formula (IV) given above is anhydro-5,5'-dichloro-3,3'-bis(n-sulphobutyl)-9-ethyloxacarbocyanine hydroxide or anhydro-5,5'-dichloro-3,3'-bis(n-sulphopropyl)-9-ethyloxacarbo-cyanine hydroxide. It has been established that silver halide emulsion crystals prepared in silica, spectrally sensitised with the preferred oxacarbocyanines show higher absorption signals in the spectra of their J-aggregates than corresponding silver halide crystals prepared in gelatin for the same surface coverage.
  • a controll solution with colloidal silica particles in the absence of silver halide crystals and in the presence of the same spectral sensitiser doesn't show the presence of J-aggregates.
  • a benzimidazolocarbocyanine spectral sensitiser is used together with a sensitiser according to the formula (IV).
  • a suitable mixture of spectral sensitisers that is advantageously applied is anhydro-5,5'-dichloro-3,3'-bis(n-sulphobutyl)-9-ethyl oxacarbocyanine or anhydro-5,5'-dichloro-3,3'-bis(n-sulphopropyl)-9-ethyloxacarbo-cyanine together with anhydro-5,5'-dicyano- 1,1'-diethyl-3,3'-di(2-acetoxyethyl)ethyl-imidacarbocyanine provided with suitable charge correcting ions for the respective compounds.
  • Emulsion layers coated with emulsions having crystals prepared in accordance with the method of the present invention, and more particularly thin emulsion layers, are showing remarkable improvements concerning both resistance to stress and rapid processability if compared with conventional emulsions prepared in gelatinous medium. As the ratio by weight of gelatin to silver halide decreases more pronounced pressure marks can be expected.
  • Silver halide photographic materials comprising light-sensitive emulsion layers comprising crystals prepared according to the method according to this invention are further fundamentally different from materials described e.g. in JP-A 04 340 951, wherein colloidal silica is used: although being advantageous with respect to pressure sensitivity, the colloidal silica used therein is not present as a protective colloid in the preparation of silver halide crystals but as a simple additive in light-sensitive layers comprising silver halide grains with a selenium compound.
  • Light-sensitive silver halide photographic materials according to the present invention however do comprise at least one hydrophilic light-sensitive silver halide emulsion layer from an emulsion prepared according to the method as set forth in the description hereinbefore.
  • said materials comprise an amount of hydrogen-bridge forming polymer and silver halide in a weight ratio of from 0 to 0.40 and silica to silver halide in a weight ratio of from 0.01 to 0.30, and more preferably, as has been set forth in the application concurrently filed herewith, from 0.01 to 0.10, said amount of silver halide being expressed as an equivalent amount of silver nitrate.
  • the photographic silver halide emulsions prepared according to the method of this invention can be used in various types of photographic elements such as i.a. in photographic elements for so-called amateur and professional photography, for graphic arts, diffusion transfer reversal photographic elements, low-speed and high-speed photographic elements, X-ray materials, micrographic materials, photothermographic elements, direct-positive elements, etc..
  • the photographic silver halide emulsions are used in X-ray materials: single-side coated as well as (symmetrically or asymmetrically) duplitized materials, used in a system in combination with (identical or differing) intensifying phosphor screens.
  • single-side coated materials they can be used as laser films which are nowadays desired hardcopy materials for use in diagnostic imaging.
  • Emulsion A Emulsion A
  • a nucleation step was performed by introducing solution A and solution B1 simultaneously in dispersion medium C both at a flow rate of 60 ml/min during 30 seconds. After a physical ripening time of 19 min 111 ml of 15 % silica sol 'Kieselsol 500' (trademarked product of Bayer AG) and 37 ml of a 5 % solution of co-stabilising phosphonium compound (Phen) 3 -P + -CH 2 -CH 2 OH.Cl - , wherein Phen represents phenyl were added to solution C with 302 ml of demineralised water. The pH value was readjusted to a value of 3.0 and the solution was stirred for another 5 minutes.
  • Phen co-stabilising phosphonium compound
  • the flow rate of solution A was increased linearly over a period of 29 minutes to 7 ml/min, while the flow rate of solution B1 was increasing in order to maintain the said constant mV-value.
  • the flow rate of solution A was increased linearly over a period of 41 minutes and 22 seconds to 12.5 ml/min, while the flow rate of solution B2 was increased in order to maintain the constant mV-value.
  • the thus obtained emulsion comprising silver bromoiodide tabular grains having 1 mole % of iodide ions based on silver, comprised a high percentage by number (at least 90 %) of tabular grains, having an aspect ratio of more than 5 which was counted from the corresponding electron microscopic photographs, having a mean ECD (equivalent circular diameter) of 1,14 ⁇ m and a mean thickness of 0.130 ⁇ m.
  • ECD equivalent circular diameter
  • the emulsion was divided in several portions (1 - 5) and chemically ripened as follows.
  • the emulsion was ripened with sulphur and gold ions. Amounts of ripening agents were adapted to the crystal size of the emulsion crystals.
  • Chemical ripening agents were gold thiocyanate, sodium thiosulphate and toluene thiosulphonic acid, which was used as predigestion agent.
  • the said amounts of each chemical ripening agent were optimised in order to obtain an optimal fog-sensitivity relationship after 4 hours at 50°C.
  • the emulsions were ripened with sulphur, gold and selenium. Amounts of ripening agents were adapted to the crystal size of the emulsion.
  • Chemical ripening agents were gold thiocyanate, sodium thiosulphate, triphenylphosphorselenide and toluene thiosulphonic acid which was used as predigestion agent. Amounts of each chemical ripening agent were varied as set forth in Table 1, and the time of ripening was adjusted in order to obtain an optimal fog-sensitivity relationship.
  • the chemically sensitised emulsions 1 to 5 were stabilised with 1-p-carboxy-phenyl-5-mercaptotetrazole.
  • the emulsions were coated in a hydrophilic coating layer on a polyester support and were illuminated in the wet state. After drying the sensitivity was measured with a densitometer.
  • silver bromoiodide grains having a cubic habit were prepared in silica sol as a protective colloid.
  • a photographic silver iodobromide emulsion containing 1.0 mole % of silver iodide was prepared by the double jet method in a vessel containing 642 ml of demineralised water, 300 ml of 15 % silica sol 'Kieselsol 500' (trademarked product of Bayer AG), 225 mg of 3,6-dithio-1,8-octanediol as a grain growth accelerator, and 72 ml of a 5 % solution of co-stabilising phosphonium compound (Phen) 3 -P + -CH 2 -CH 2 OH.Cl - , wherein Phen represents phenyl.
  • the temperature was stabilised at 50°C and the pH value was adjusted to a value of 3.0.
  • a silver nitrate solution (2.94 M) was added to the reaction vessel at a constant flow rate of 8 ml/min.
  • Mixing of both salt solutions was performed with central stirring means at 500 rpm.
  • the flow rate of the silver nitrate solution was increased continously up to 16 ml/min during 80 minutes.
  • the mixed halide solution was further added at an addition rate in order to maintain the same constant pAg value.
  • the emulsions obtained comprised crystals having a ⁇ 100 ⁇ cubic habit and had an average grain size based on volume of around 0.60 ⁇ m.
  • the homogeneity of the silver halide grain distribution expressed as the variation on the mean grain size is equal to around 20 %.
  • the obtained cubic AgBr(I) emulsion precipitated in silica was then divided in 3 separate portions.
  • Chemical ripening agents were gold thiocyanate, sodium thiosulphate and toluene thiosulphonic acid which was used as a predigestion agent.
  • anhydro- 5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyloxacarbo-cyanine hydroxide and anhydro-5,5'-dicyano- 1,1'-diethyl-3,3'-di(2-acetoxyethyl)ethyl-imidacarbocyanine bromide were added in amounts of 0.40 mmole and 0.24 mmole per mole of silver nitrate respectively.
  • Chemical ripening agents for sample No. 2 and sample No. 3 were gold thiocyanate, sodium thiosulphate, triphenylphosphorselenide and toluene thiosulphonic acid which was again used as predigestion agent. Amounts of each chemical ripening agent were varied as set forth in Table 1, and the time of ripening was adjusted in order to obtain an optimal fog-sensitivity relationship. Spectral sensitisation was performed in the same way as for sample No. 1 hereinbefore.
  • the chemically sensitised emulsions (samples Nos. 1 to 3) were coated in a hydrophilic coating layer on a polyester support and were illuminated in the wet state. After drying the sensitivity was measured with a densitometer.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
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EP96202612A 1996-09-18 1996-09-18 Crystaux d'émulsion sensibilisés à l'halogénure d'argent avec de la silice colloidale en tant que seule colloide protecteur pendant la précipitation Withdrawn EP0831363A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP96202612A EP0831363A1 (fr) 1996-09-18 1996-09-18 Crystaux d'émulsion sensibilisés à l'halogénure d'argent avec de la silice colloidale en tant que seule colloide protecteur pendant la précipitation
JP27051097A JPH10104770A (ja) 1996-09-18 1997-09-16 保護コロイドとしてのコロイドシリカでハロゲン化銀結晶を増感した感光性乳剤を製造する方法

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EP96202612A EP0831363A1 (fr) 1996-09-18 1996-09-18 Crystaux d'émulsion sensibilisés à l'halogénure d'argent avec de la silice colloidale en tant que seule colloide protecteur pendant la précipitation

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0428041A1 (fr) * 1989-11-06 1991-05-22 Fuji Photo Film Co., Ltd. Emulsion photographique à l'halogénure d'argent
EP0443453A1 (fr) * 1990-02-15 1991-08-28 Fuji Photo Film Co., Ltd. Emulsion photographique à l'halogénure d'argent et matériau photographique sensible à la lumière l'utilisant
JPH04340951A (ja) * 1991-05-17 1992-11-27 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料及びその現像処理方法
JPH05313293A (ja) * 1992-05-08 1993-11-26 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料及びその現像処理方法
EP0677773A1 (fr) * 1994-04-06 1995-10-18 Agfa-Gevaert N.V. Emulsions à l'halogénure d'argent comprenant des cristaux tabulaires et méthode de traitement de ces émulsions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0428041A1 (fr) * 1989-11-06 1991-05-22 Fuji Photo Film Co., Ltd. Emulsion photographique à l'halogénure d'argent
EP0443453A1 (fr) * 1990-02-15 1991-08-28 Fuji Photo Film Co., Ltd. Emulsion photographique à l'halogénure d'argent et matériau photographique sensible à la lumière l'utilisant
JPH04340951A (ja) * 1991-05-17 1992-11-27 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料及びその現像処理方法
JPH05313293A (ja) * 1992-05-08 1993-11-26 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料及びその現像処理方法
EP0677773A1 (fr) * 1994-04-06 1995-10-18 Agfa-Gevaert N.V. Emulsions à l'halogénure d'argent comprenant des cristaux tabulaires et méthode de traitement de ces émulsions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section PQ Week 9302, Derwent World Patents Index; Class P83, AN 93-013262, XP002027557 *
DATABASE WPI Section PQ Week 9401, Derwent World Patents Index; Class P83, AN 94-002672, XP002027558 *

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