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
  • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/16—X-ray, infrared, or ultraviolet ray processes
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/16—X-ray, infrared, or ultraviolet ray processes
  • G03C5/164—Infrared processes

Definitions

• the invention relates to a spectrally sensitized photographic silver halide recording material which has a reduced decrease in sensitivity during aging and a process for the production of such spectrally sensitized photographic silver halide recording materials.
• Silver halide photographic materials have a variety of uses in the graphic arts. Examples of this are the production of so-called color separations from colored templates. These color separations can then be used directly or indirectly as templates for the production of printing plates such as offset printing plates and flexographic printing plates.
• a silver halide emulsion is usually spectrally sensitized with one or more suitable dyes.
• Spectral sensitization is understood by the person skilled in the art to extend the practically usable sensitivity range of silver halide emulsions and silver halide emulsion layers to longer wavelengths by coloring the silver halide crystals with dyes which absorb light of these wavelengths and make them usable for the formation of the latent image.
• This spectral sensitization increases the sensitivity of a silver halide emulsion to light of certain wavelengths. Examples of such spectral sensitizing dyes and their use in photographic silver halide emulsions are in the monograph "Spectral Sensitization" by H. Meier, The Focal Press, London and New York, (1968) and in "Ullmann's Encyclopedia of Industrial Chemistry", fifth edition, Volume 20A, VCH-Verlagsgesellschaft mbH, Weinheim (1992), on pages 10 to 17.
• Spectral sensitizers for red and / or infrared-sensitized silver halide recording materials and the amounts to be used thereof are known to the person skilled in the art. Such sensitizers increase the sensitivity of silver halide emulsions to light from a wavelength of 600 nm.
• suitable sensitizing dyes are sensitizing in the patents US 4,917,997 and US 3,682,640 and in Research Disclosure, vol. 308, number 308119 (December 1989) section IV A " dyes "and the quotations contained therein. [Research Disclosure is published by Kenneth Mason Publications Ltd., Dudley Annex, 21a North Street, Elmsworth, Hampshire P010 7DQ, England.]
• Suitable spectrally sensitizing dyes for the infrared spectral range are described, for example, in US Pat. No. 5,009,992.
• a process for producing silver images using silver halide recording materials containing silver halide emulsion layer sensitized with red sensitizing dyes, which comprises wet processing, is described, for example, in EP-A 04 27 892.
• a disadvantage of silver halide recording materials which are spectrally sensitized with at least one dye is the decrease in sensitivity during their storage. This interferes with their use, since it can lead to fluctuations in the quality of the images produced from them. This effect occurs particularly in the case of photographic recording materials which are spectrally sensitized to wavelengths of at least 600 nm.
• Such recording materials are used in exposure devices which are suitable for exposing silver halide recording materials and which use helium / neon lasers, infrared lasers or red-emitting laser diodes as the light source.
• reductones such as ascorbic acid and its derivatives in silver halide emulsions
• reductones such as ascorbic acid and its derivatives in silver halide emulsions
• EP-A 04 04 142 and EP-A 03 78 841 the addition of ascorbic acid and ascorbic acid derivatives in EP-A 04 04 142 and EP-A 03 78 841 to silver halide emulsions for reduction sensitization is proposed.
• Ascorbic acid has also been proposed as a developer substance in the form of an additive in an auxiliary layer in amounts of more than 1.2 g / m 2 in FR-A 1 591 741.
• Ascorbic acid in an auxiliary layer of a silver halide photographic material has a deleterious influence on its photographic properties.
• the object of the present invention is therefore to provide a photographic recording material which contains at least one silver halide emulsion layer which has been spectrally sensitized with at least one dye and which has a lower loss in sensitivity over time during storage.
• the object is achieved by a photographic recording material according to claim 1 and a method for producing such a material according to claim 8.
• Suitable reductones are, for example, isoascorbic acid, reductic acid, triose reductone, ascorbic acid and all stereoisomers of the aforementioned compounds and / or their optionally substituted ammonium and metal salts.
• Suitable reductone derivatives are, for example, N, N'-dialkylaminohexose reductones as described, for example, in GB-1,255,084 and ascorbic acid derivatives such as, for example, ascorbic acid 6-acetate, ascorbic acid 6-benzoate, ascorbic acid 5,6-diacetate, ascorbic acid 5,6-O-isopropylidene and ascorbic acid 6-palmitate and all stereoisomers of the aforementioned compounds and / or their optionally substituted ammonium and metal salts.
• Reducone derivatives on the other hand, are unsuitable if they no longer have the reducing properties of the reductones.
• metal salts one-, two- and three-valent cations are used as cations, for example.
• metals sodium, potassium, magnesium, calcium, iron and strontium.
• Ascorbic acid and ascorbic acid derivatives their stereoisomers and / or their alkali metal salts are preferred.
• reductones and reductone derivatives can also be used according to the invention in the form of water-soluble salts.
• An example of this is the sodium salt of ascorbic acid.
• one or more reductones and / or reductone derivatives can be used.
• the reductones and / or reductone derivatives can be contained in various auxiliary layers of the photographic silver sharkide recording material.
• at least one reductone and / or reductone derivative is contained in a protective layer lying over the silver halide emulsion layer.
• the reductones and / or reductone derivatives can also be contained next to one another in several auxiliary layers of a photographic silver halide recording material.
• a suitable amount of the sum of reductones and / or reductone derivatives in an auxiliary layer is at a basis weight between 0.0001 and 0.5 g / m2.
• the preferred range is a weight per unit area between 0.001 and 0.1 g / m2, the range between 0.005 and 0.05 g / m2 being particularly preferred.
• the upper limit for a suitable amount of the sum of the reductones and / or reductone derivatives results, inter alia, from an intolerable deterioration in photographic properties such as, for example, fog or gradation.
• Such quantities of reductones and / or reductone derivatives which can largely assume the function of the developer are therefore not suitable for the application according to the invention.
• the protective layer is the layer that is furthest away from the base and does not contain any silver halide.
• such protective layers contain, for example, gelatin, which can be produced both by acid and alkaline digestion and, if appropriate, surface-active substances also other substances which influence the chemical, physical and mechanical properties of the photographic recording material.
• these substances include, for example, lubricants, perfluoroalkyl group-containing surface-coating substances, latices (polymeric organic particles), stabilizers, finely divided SiO 2 dispersions, matting agents (spacers), curing agents, antistatic substances and preservatives.
• a spectrally sensitized silver halide recording material is used, which between an spectrally sensitized silver halide emulsion layer and an auxiliary layer according to the invention on the same side of the carrier material and containing at least one reductone and / or reductone derivative also contains at least one intermediate layer containing at least gelatin with a basis weight of Contains 0.05 to 1.0 g of gelatin per square meter.
• a silver halide recording material in which at least one reductone and / or reductone derivative is contained in the protective layer is particularly preferred.
• a spectrally sensitized silver halide recording material which contains one or more spectrally sensitized silver halide emulsion layers on only one side of the support material and in which the auxiliary layer according to the invention containing at least one reductone and / or reductone derivative is located on the other side of the support material .
• Additional auxiliary layers containing at least one reductone and / or reductone derivative may be located on the side of the carrier material containing one or more spectrally sensitized silver halide emulsion layers.
• the photographic emulsions can be prepared from soluble silver salts and soluble halides by various methods.
• Metal ions such as cadmium, zinc, thallium, mercury, iridium, rhodium and iron or their complexes may be present during the production and / or physical ripening of the silver halide emulsion.
• the soluble salts are removed from the emulsion, for example by pasta and washing, by flaking and washing, by ultrafiltration or by means of ion exchange.
• the silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached.
• chemical sensitizers such as active gelatin, sulfur, selenium or tellurium compounds, salts or complexes of gold, platinum, rhodium, palladium, iridium, osmium, rhenium, ruthenium can be used alone or in combination. Procedures are described, for example, by H.
• a compound suitable for reduction sensitization can be added to the silver halide emulsion in the course of the preparation.
• reduction sensitization here means that a reducing agent is added to the emulsion and thereby the photosensitivity of the silver halide emulsion is increased.
• the addition can take place at any time in the production process, for example during the precipitation of the silver halide and before, during or after chemical ripening.
• Suitable reducing agents are, for example, tin (II) chloride, hydrazine and certain hydrazine derivatives, glutardialdehyde, glutardialdehyde bisulfite, formamidinesulfinic acid, thiourea dioxide, silanes, reductones such as ascorbic acid, ascorbic acid derivatives and comparable reducing sugars, polyamines such as, for example, dimethylene triamine and boramine Dimethylaminoborane.
• tin (II) chloride hydrazine and certain hydrazine derivatives
• glutardialdehyde glutardialdehyde bisulfite
• formamidinesulfinic acid thiourea dioxide
• silanes silanes
• reductones such as ascorbic acid, ascorbic acid derivatives and comparable reducing sugars
• polyamines such as, for example, dimethylene triamine and boramine Dimethylaminoborane.
• the reduction sensitization can also be brought about by treating the emulsion with gaseous hydrogen or by digesting the emulsion with excess silver ions.
• the layers of the photographic recording material can contain substances for stabilizing the emulsion against fog or for stabilizing other photographic properties such as, for example, sensitivity.
• Materials include, for example bromides, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, Mercaptothiodiazole, chlorobenzimidazoles, bromobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxazolinethione, Azaindolizine as Thazaindolizine and Tetraazaindolizine as the particularly preferred 5- Hydroxy-7-methyl-1,3,4, -triazaindolizine, and mercaptotetrazoles such as 1-phenyl-5-mercaptotetrazole.
• the layers containing hydrophilic binders can contain organic or inorganic hardening agents.
• the hardening of a layer can also be effected by covering the layer to be hardened with a layer which contains a diffusible hardening agent, as is described, for example, in DE-A 38 36 945.
• the curing agent can be added in the course of the preparation of emulsion solutions and / or casting solutions for auxiliary layers. Another possible form of addition is to inject a solution of the hardening agent into at least one emulsion or casting solution while it is being transported from the storage kettle to the casting device.
• suitable solvents for this purpose are other water-miscible organic solvents such as, for example, ethanol, acetone, dimethyl sulfoxide or 1,4-dioxane.
• substances or mixtures of substances can be present which adjust and / or buffer the pH of the hardener solution.
• An example of this is the borate buffer described in DE-C 28 20 108.
• hardening agents which can be used in photographic recording materials are chromium salts such as chromium alum, aldehydes such as formaldehyde, glyoxal and glutardialdehyde, N-methylol compounds such as N, N'-dimethylolurea, reactive vinyl group-bearing compounds such as 1,3-bis- (vinylsulfonyl) -2-propanol , Bis (vinylsulfonyl) methyl ether, N, N ', N''- trisacryloylhexahydrotriazine, polymeric curing agents as described for example in DE-C 32 23 621, 1,3-bis-carbamoylimidazolium compounds as described in DE-B 41 19 982 or carbamoylpyrimidinium compounds as described for example in DE-C 23 17 677.
• chromium salts such as chromium alum
• aldehydes such as formaldeh
• Two or more curing agents can also be used side by side.
• formaldehyde is at least partially used as the curing agent used. It is particularly preferred to use at least 20 mol% of formaldehyde, based on the total amount of hardener.
• the amount of a sensitizing dye or a combination of dyes which is necessary for the maximally achievable sensitization of the silver halide emulsion in the absorption spectrum of the dye can easily be determined by a person skilled in the art with the aid of suitable experiments.
• Spectral sensitizers in the silver halide emulsion can include, for example, cyanine dyes, merocyanine dyes, oxonol dyes, hemioxonol dyes, hemicyanine dyes, styryl dyes.
• a spectral sensitizer alone or a combination of at least two spectral sensitizers can be used.
• Such spectral sensitizers or combinations of spectral sensitizers are usually used in silver halide emulsions in an amount of 20 mg to 3.0 g per mole of silver halide.
• spectral sensitizers for sensitizing silver halide recording materials for red and / or infrared light of a wavelength of at least 600 nm is preferred.
• spectrally sensitizing dyes which sensitize silver halide recording materials to light of a wavelength of 600 to 1050 nm are particularly preferred.
• Cyanine dyes and merocyanine dyes are particularly preferred.
• the silver halide emulsion can be subjected to a process for supersensitization using supersensitizers such as, for example, ascorbic acid in conjunction with dyes and optionally other substances.
• supersensitizers such as, for example, ascorbic acid
• reductones and / or reductone derivatives according to the invention is advantageous.
• the photographic recording material can each have one or more silver halide emulsion layers on one or both sides of the support material.
• the photographic recording material contains at least one silver halide emulsion layer on only one side of the support material.
• Silver coating is understood to mean the weight of silver in the form of its ions in the layers containing the silver halide crystals, based on the unit area of the silver halide photographic material.
• the values for the silver job are given in grams / square meter and relate to the sum of all layers of the recording material containing silver halide.
• the amount of silver applied to spectrally sensitized silver halide recording materials is usually in the range between 0.5 g / m2 and 8 g / m2.
• the silver halide crystals in the silver halide emulsion can have a regular crystal shape such as, for example, cubes, octahedra or cubo-octahedra, or a less regular shape such as plates, single twins with (111) and / or (100) boundary surfaces or spheres. Furthermore, silver halide emulsions can also contain mixtures of at least two of these crystal forms.
• Cubic silver halide crystals with an average grain volume of 0.001 to 1.0 ⁇ m3 are preferably used.
• the mean grain diameter of a silver halide emulsion for calculating the grain volume can be measured with the aid of various methods, for example with the aid of electron microscope images of the corresponding emulsion.
• the average grain volume of a silver halide emulsion can be determined using the method described in DE 20 25 147.
• the silver halide emulsions may contain chloride, bromide, iodide or a combination of at least two of them as the halide.
• a silver bromide iodide emulsion with up to 5 mol% iodide is suitable, for example.
• Silver halide emulsions are preferably used in which the chloride content is at least 70 mol% of the total amount of the halides and up to 3 mol% iodide can also be present.
• alkaline digested bovine bone gelatin is preferably used as a protective colloid for the silver halide crystals in the emulsion layer and hydrophilic binder. This can be exchanged for ions.
• hydrophilic binders can also be used in the various layers of the silver halide recording material.
• hydrophilic binders are synthetic polymers such as polymers or copolymers of vinyl alcohol, N-vinylpyrrolidone, acrylamide, acrylic acid, methacrylic acid, vinylimidazole, vinylpyrazole and natural polymers such as casein, gelatin (acidic or alkaline digested, made from bovine bones or pig skin), cellulose and cellulose derivatives, alginates, albumin, starch, and modified polymers such as hydroxyethyl cellulose, hydrolyzed gelatin, chemically modified gelatin as described for example in EP-A 03 75 522, chemically modified and hydrolyzed gelatin as described for example in DE-B 21 66 605 and US-A 3,837,861.
• the hydrophilic binder may be contained in the silver halide emulsion layers and other auxiliary layers such as protective layers, adhesive layers, intermediate layers or non-light-sensitive layers.
• binders can be contained in the layers of the photographic recording material.
• binders are matting agents or latices (polymeric organic particles) which are introduced into the corresponding casting solution in the form of aqueous dispersions which are usually stabilized by wetting agents.
• the silver halide emulsion and the mixtures for the production of auxiliary layers can contain surface-active substances for various purposes, for example as coating aids, to prevent electrostatic charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve photographic properties Characteristics (e.g. acceleration of development, high contrast, sensitization).
• surface-active substances for various purposes, for example as coating aids, to prevent electrostatic charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve photographic properties Characteristics (e.g. acceleration of development, high contrast, sensitization).
• nonionic surfactants contain soft oligo- or polyoxyalkylene groups, glycerol compounds and glycidol compounds, cationic surfactants, for example higher alkylamines, quaternary ammonium salts, pyridine compounds, and other heterocyclic compounds, sulphonium compounds or Phosphonium compounds, anionic surfactants containing an acid group, for example carboxylic acid, phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants such as amino acid and aminosulfonic acid compounds, and sulfur and phosphoric acid esters of an amino alcohol.
• nonionic surfactants contain soft oligo- or polyoxyalkylene groups, glycerol compounds and glycidol compounds, cationic surfactants, for example higher alkylamines, quaternary ammonium salts, pyridine compounds, and other heterocyclic compounds, sulphonium compounds or Phosphonium compounds, anionic surfactants containing an acid group
• the layers of the photographic recording material can contain filter dyes such as oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, cyanine dyes, azomethine dyes, triarylmethane dyes, phthalocyanines and azo dyes.
• filter dyes such as oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, cyanine dyes, azomethine dyes, triarylmethane dyes, phthalocyanines and azo dyes.
• their compatibility is a prerequisite for the use of such filter dyes in the auxiliary layer containing reductone with the corresponding reductone. For example, there is an intolerance if the two substances react chemically with one another.
• the carrier material of the photographic recording material can consist of an optionally resin-coated paper, an optionally coated aluminum or a transparent and optionally colored plastic film.
• a plastic film can be produced, for example, from plastics such as polyethylene terephthalate, cellulose acetate, cellulose acetate butyrate, polystyrene or polycarbonate.
• Carrier materials made of aluminum are used, for example, in the production of offset printing plates.
• the surface of the carrier material is preferably treated by a corona discharge before a first coating in order to improve the adhesion properties.
• Various casting methods can be used to make the photographic material. Examples of this are curtain casting, cascade casting, dip casting, wash-on casting, slot casting. If necessary, several layers can be applied simultaneously.
• the mixture containing at least one reductone and / or reductone derivative to form a non-light-sensitive auxiliary layer according to the invention can be applied before, during and / or after coating an optionally coated support material with a spectrally sensitized silver halide emulsion.
• the spectrally sensitized silver halide emulsion and the mixture containing at least one reductone and / or reductone derivative are simultaneously applied to a support material to form an auxiliary layer.
• the spectrally sensitized silver halide recording material according to the invention can be used in all areas of silver halide photography. Examples of this are negative and direct positive black and white photography, positive and negative color photography, production of offset printing plates, and silver salt diffusion processes. Preferred is the use for the production of silver images by wet processing, as described in EP-A 04 27 892.
• a silver chloride bromide emulsion (80 mol% chloride, 20 mol% bromide) with cubic silver halide grains with an edge length of 0.2 ⁇ m was prepared, freed from soluble salts by precipitation and washing, matured in the presence of a sulfur compound, a gold compound and potassium rhodanide and for spectrally sensitized the wavelength range from 620 to 700 nm with a commercially available cyanine dye with the structure shown in EP-A 04 27 892 under formula (I-01).
• Samples of the emulsion thus prepared were mixed with pouring aids and with such amounts of ascorbic acid and applied to a carrier material containing a polyester film in such a way that the values given in Table 1 for the basis weight of the ascorbic acid in the emulsion layer with a basis weight of the applied silver of 4. 0 g / m2 was achieved.
• a protective layer containing gelatin, casting aids, matting agents, formaldehyde and ascorbic acid was applied over the silver halide emission in such a way that the values given in Table 1 for the weight per unit area of ascorbic acid were achieved (tests 1 to 4) and the weight per unit area of the gelatin in protective layer 0, Was 8 g / m2.
• Samples of the photographic material thus prepared were exposed after 2 days or after storage for 3 months at a temperature of 20 ° C (exposure time 0.0001 seconds) in a roll developing machine under development at 35 ° C in 25 seconds in the commercially available developer " CUFD "from DuPont and determines the sensitivity of the material produced in this way.
• the absolute values for sensitivity are shown in 1/10 logarithmic units and the percentage loss of sensitivity after 3 months in linear units in Table 1.
• a silver halide emulsion was prepared analogously to Example 1, ripened and spectrally sensitized for the infrared wavelength range from 740 to 790 nm with a commercially available cyanine dye with the structure shown in US Pat. No. 5,009,992 under formula (II-1).
• Samples of the emulsion thus prepared were mixed with pouring aids and with different amounts of ascorbic acid and applied to a carrier material containing a polyester film in such a way that the values given in Table 2 for the weight per unit area of ascorbic acid in the emulsion layer for a weight per unit area of the applied silver of 4. 0 g / m2 was achieved (experiments 5 to 8).
• a protective layer containing gelatin, casting aids, matting agents, formaldehyde and ascorbic acid was applied over the silver halide emulsion in such a way that the values given in Table 2 for the weight per unit area of the ascorbic acid were achieved and the weight per unit area of the gelatin in the protective layer was 0.8 g / m 2 in each case .
• a recording material (test 9) with the above-described silver halide emulsion, the above-described mixture for producing a protective layer and a mixture for producing an intermediate layer was produced in such a way that the silver coating was 4.0 g / m 2, the basis weight of the gelatin in the protective layer 0 , 5 g / m2 and the gelatin application of the intermediate layer was 0.4 g / m2.
• the mixture for producing the intermediate layer contained wetting agents and as much ascorbic acid so that when the recording material was produced with the aforementioned basis weight of gelatin in the intermediate layer, the intermediate layer contained 2.2 mg / m 2 ascorbic acid.
• the amount of ascorbic acid contained in the silver halide emulsion layer and the protective layer is shown in Table 2.
• Experiment 9 shows that the presence of a gelatin-containing layer containing only a little ascorbic acid between the spectrally sensitized silver halide layer and the auxiliary layer containing ascorbic acid additionally reduces the age-related decrease in sensitivity.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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• 1994
  • 1994-12-02 DE DE4442876A patent/DE4442876A1/de not_active Withdrawn
• 1995
  • 1995-11-27 EP EP95118639A patent/EP0715210A3/fr not_active Withdrawn
  • 1995-12-04 JP JP7346554A patent/JPH08234357A/ja active Pending

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