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
  • G03C1/915—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means using mechanical or physical means therefor, e.g. corona
• • 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
  • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
  • G03C1/7954—Polyesters

Definitions

• the present invention relates to a silver halide photographic material comprising a glow discharge-treated polyester having a glass transition temperature of 90 °C to 200 °C as a support.
• TAC triacetyl cellulose
• PET polyester polymer such as polyethylene terephthalate
• photographic light-sensitive materials are in the form of sheet film as in X-ray film, plate-making film and cut film or roll film as in color or black-and-white negative roll to be mounted in a cartridge having a width of 35 mm or less.
• TAC to be used as the support for roll films exhibits a high transparency and an excellent decurlability after development.
• PET films are excellent in mechanical strength and dimensional stability but are left much curled when unwound after development. This poor handleability puts restrictions on its application range despite its excellent properties.
• the photographic light-sensitive materials have found a variety of applications. For example, the reduction in the size of cameras, the increase in the film delivery speed upon picture taking and the increase in the magnification have been required. This requires a support having a high strength, a good dimensional stability and a small thickness.
• One of the two problems is to inhibit the reduction in the dynamic strength accompanied by the reduction in the thickness of the film.
• the other problem is a strong curl developed with time during storage due to the reduction in the size of the spool.
• JP-A-51-16358 As an approach for reducing the curl of the polyester film there has been known a method as disclosed in JP-A-51-16358 (The term "JP-A” as used herein means an unexamined published Japanese patent application") and U.S. Patent 4,141,735.
• the polyester support can easily be electrically charged upon picture taking or when carried in an automatic developing machine. When discharged, it may cause fogging.
• the state-of-the-art antistatic method is disadvantageous in that since the material used elutes with the processing solution, the antistatic properties are eliminated after development. Thus, dust attached to the material due to electric charge appears on the print.
• a silver halide photographic material comprising at least one light-sensitive layer on a polyester support
• the polyester support is a glow discharge-treated polyester support having a glass transition temperature of 90 °C to 200 °C.
• Tg of the polyester support to be used in the present invention is in the range of 90 °C to 200 °C.
• the polyester having such a Tg range is formed by the following dibasic acids and diols.
• dibasic acids which can be used in the present invention include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, scuccinic acid, glutaric acid, adipic acid, sebasic acid, succinic anhydride, maleic acid, fumaric acid, maleic anhydride, itaconic acid, citraconic anhydride, tetrahydrophthalic anhydride, diphenylene-p,p'-dicarbonic acid, tetrachlorophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid,
• diols which can be used in the present invention include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptaned
• polyesters which can be used in the present invention include homopolymers such as polyethylene naphthalate (PEN), polyethylene terephthalate and polycyclohexanedimethanol terephthalate (PCT), those obtained by the copolymerization of, 2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), and biphenyl-4,4'-dicarboxylic acid (PPDC) as dicarboxylic acids, ethylene glycol (EG), cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), bisphenol A (BPA), and biphenol (BP) as diols, and parahydroxybenzoic acid (PH
• polyesters Preferred among these polyesters are copolymers such as copolymer of naphthalenedicarboxylic acid, terephthalic acid and ethylene glycol (mixing molar proportion of naphthalenedicarboxylic acid and terephthalic acid is preferably 0.3 : 0.7 to 1 : 0, more preferably 0.5 : 0.5 to 0.8 : 0.2), copolymer of terepthalic acid, ethylene glycol and bisphenol A (mixing molar proportion of ethylene glycol and bisphenol A is preferably 0.6 : 0.4 to 0 : 1, more preferably 0.5 : 0.5 to 0.1 : 0.9), copolymer of isophthalic acid, biphenyl-4,4'-dicarboxylic acid, terepthalic acid and ethylene glycol (molar proportion of isophthalic acid and biphenyl-4,4'-dicarboxylic acid to terepthalic acid as 1 are preferably 0.1 to 2 and 0.1 to 4, more
• PEN is most preferred among these polyesters.
• PEN exhibits a high dynamic strength, particularly elastic modulus, and a glass transition temperature as high as about 120 °C.
• These homopolymers and copolymers can be synthesized by any known polyester preparation method.
• an acid component is allowed to undergo direct esterification reaction with with a glycol component to synthesize a homopolymer or copolymer.
• a dialkylester is used as an acid component, it is allowed to undergo ester exchange reaction with a glycol component, and the reaction sysytem is then heated under reduced pressure to remove excess glycol component to synthesize a homopolymer or copolymer.
• the acid component may be reacted with a glycol component in the form of acid halide.
• the reaction may be effected in the presence of an ester exchange reaction catalyst or polymerization reaction catalyst or with a heat stabilizer added to the system.
• an ester exchange reaction catalyst or polymerization reaction catalyst or with a heat stabilizer added to the system.
• a heat stabilizer added to the system.
• the average molecular weight of these polyesters is preferably in the range of about 5,000 to 100,000.
• the blend of polymers thus obtained can be easily formed in accordance with methods as disclosed in JP-A-49-5482, 64-4325, and 3-192718, and Research Disclosure Nos. 283,739-41, 284,779-82, and 294,807-14.
• the object of glow discharge treatment is to fulfill various requirements for the support to be treated, such as enhancement of adhesive properties and mar resistance and inhibition of yellowing, at the same time.
• supports which have been obtained by subjecting polyethylene terephthalate support materials of the present invention to heat treatment at a temperature of from 50 °C to the glass transition temperature thereof it is an important object to suppress blocking and yellowing (represented by the comparison of absorbance at 400 nm between before and after treatment) within a 7 % increase from that before the heat treatment at the same time with the fulfillment of the other requirements.
• glow discharge treatment is especially effective for the polyester support having a glass transition temperature of 90 °C to 200 °C of the present invention, while it is not considered that glow discharge treatment is especially effective for PET.
• the glow discharge treatment may be conducted under arbitrary conditions effectively, but the glow discharge treatment is preferably conducted in the presence of water vapor.
• the glow discharge treatment efficiently provides sufficient adhesive properties in a short period of time, inhibiting yellowing.
• the percent partial pressure of water vapor in the presence of which the glow discharge treatment is conducted is preferably from 10 % to 100 %, more preferably 40 % to 90 % based on the treatment atmosphere. This is because that if this value falls below 10 %, it is difficult to obtain sufficient adhesive properties.
• the gas other than water vapor is air containing oxygen, nitrogen, etc.
• the quantitative introduction of water vapor into the atmosphere for glow discharge treatment can be accomplished by introducing the gas through a sampling tube mounted on the glow discharge treatment apparatus into a quadrupole type mass analyzer by which the composition of the gas is assayed.
• a glow discharge treatment is effected with various gases (e.g., oxgen gas, nitrogen gas, and argon gas) being introdued into the system.
• gases e.g., oxgen gas, nitrogen gas, and argon gas
• the use of water vapor is the most efficient.
• argon gas provides an enhancement of the adhesive properties, a relatively small worsening of yellowing and a relatively small drop of mar resistance but is disadvantgageous in that argon gas is too expensive for industrial application.
• the reason why the adhesive properties of the polyester support is enhanced by the glow discharge treatment in the presence of water vapor can be believed as follows. Specifically, it is thought that water molecules activated by the glow discharge treatment react with the polyester on the surface of the polyester support, facilitating the introduction of hydroxyl groups into the polyester molecules.
• the glow discharge treatment when the glow discharge treatment is effected in the presence of oxygen, activated oxygen molecules cause carbonyl groups or ether groups to be formed on the polyester molecules on the surface of the polyester support.
• the material is normally coated with a hydrophilic polymer (e.g., gelatin) on the glow-discharged surface. Therefore, it is thought that hydroxyl group has a higher affinity for the hydrophilic polymer and can provide sufficient adhesive properties more easily than carbonyl or ether group. This probably can shorten the glow discharge treatment time, inhibiting yellowing or mar resistance drop.
• the support which has been thus preheated is then subjected to glow discharge treatment.
• Important treatment conditions to be controlled other than partial pressure of water vapor and preheating temperature of support are degree of vacuum, voltage across electrodes, etc. By properly controlling these treatment conditions, the glow discharge treatment can be effected to provide sufficient adhesive properties and mar resistance at the same time.
• the pressure under which the glow discharge treatment is effected is preferably from 0.005 to 20 Torr, more preferably 0.02 to 2 Torr. If the pressure is too low, the surface of the support cannot be sufficiently modified, making it impossible to obtain sufficient adhesive properties. On the other hand, if the pressure is too high, the surface destruction proceeds too far. Thus, as the molecular weight of the polyester molecules lowers, embrittlement proceeds, rendering the support surface brittle. This can easily cause a deterioration of adhesive properties and mar resistance.
• the glow discharge voltage is preferably from 500 to 5,000 V, more preferably 500 to 3,000 V. If the voltage is too low, the surface of the support cannot be sufficiently modified, making it impossible to obtain sufficient adhesive properties. On the other hand, if the pressure is too high, the surface of the support is denatured, causing a drop of adhesive properties and mar resistance.
• the support which has been thus subjected to glow discharge treatment is preferably immediately cooled by means of cooling roll. This is because that with the rise in the temperature the support to be treated is subject to plastic deformation due to external force that impairs the smoothness thereof or causes low molecular compounds (e.g., monomer, oligomer) to be deposited on the surface thereof and thus impairs the transparency thereof, making it impossible to put the material into practical use.
• low molecular compounds e.g., monomer, oligomer
• the percent partial pressure of water vapor in the treatment atmosphere is from 10 % to 90 %, the pressure is from 0.005 to 20 Torr, and the voltage across electrodes is from 500 V to 5,000 V.
• the discharge frequency is in the range of 0 (direct current) to several hundreds of MHz, preferably 50 Hz to 20 MHz, more preferably 50 Hz to 1 MHz, as seen in the conventional technique.
• the discharge treatment intensity may range from 0.01 KV ⁇ A ⁇ min./m2 to 5 KV ⁇ A ⁇ min./m2, preferably from 0.15 KV ⁇ A ⁇ min./m2 to 1 KV ⁇ A ⁇ min./m2, to provide a desired adhesivity.
• the gas partial pressure in the vacuum tank is determined by measuring the gas composition from peaks appearing every mass in a specimen sampled from the gas in the tank via a quadrupole type mass spectrograph (MSQ-150 available from ULVAC Japan, Ltd.) directly connected to the vacuum tank.
• MSQ-150 available from ULVAC Japan, Ltd.
• the inventor further found that if the film is subject to glow discharge treatment at the preheated state, it may be treated for a shorter period of time than at ordinary temperature to provide improvements in the film surface properties such as adhesivity and hydrophilicity and the degree of yellow coloring of the film accompanied by the vaccum glow discharge treatment can be drastically reduced.
• the preheating temperature is preferably from 50 °C to Tg, more preferably 70 °C to Tg, further preferably 90 °C to Tg. If the preheating temperature is higher than Tg, it slightly deteriorates the adhesivity of the support.
• the method for raising the temperature of the surface of the polymer in vacuo include heating by an infrared heater and heating by being brought into contact with a heat roll.
• a heat roll For example, if the surface of the film is to be heated to a temperature of 115 °C, the film has to only be brought into contact with a 115 °C heat roll for 1 second at most.
• the present invention is not limited to the foregoing heating methods, but various known heating methods can be used.
• the minimum core diameter of the conventional 135 system is 14 mm. If the minimum core diameter of the conventional 135 system is reduced to 5 to 11 mm, even a polyester support of the present invention has a curl and thus finds difficulty in travel during the development procedure.
• the photographic emulsion undergoes pressure marking (fogging), making it impossible to further reduce the diameter of the spool.
• the heat treatment at a temperature of 50 °C to less than Tg or the slow cooling from not less than Tg to less than Tg is called “post heat treatment” or “heat treatment (1)” herein.
• the heat treatment which is effected at a temperature of from Tg to Tg + 130 °C prior to the post heat treatment is called “preheat treatment” or "heat treatment (2)”.
• the preheat treatment is conducted.
• the preheat treatment is effected at a temperature of Tg or more to fully destroy the crystalline structure of the polyester support.
• the preheating temperature exceeds Tg + 130 °C, the base generally exhibits an increased fluidity, giving difficulty in handleability.
• the preheat treatment is preferably effected at a temperature of from Tg to Tg + 130 °C, more preferably from Tg + 10 °C to the crystallization point.
• the preheat treatment time needs to be 0.1 minute or more. However, the preheat treatment time exceeds 1,500 hours, the base is disadvantageously colored. Accordingly, the preheat treatment time is preferably from 0.1 minute to 1,500 hours, more preferably from 1 minute to 1 hour.
• the post heat treatment is preferably effected at a temperature of from 50 °C to less than Tg.
• the post heat treatment may be effected at a constant temperature or at a temperature being gradually lowered. More preferably, the post heat treatment is effected at a temperature being gradually lowered from not less than Tg to less than Tg as defined herein.
• the preferred time of the post heat treatment is 0.1 to 500 hours.
• the average cooling rate between Tg and Tg - 40°C is preferably from - 0.01 °C/min. to - 20 °C/min., more preferably from - 0.01 °C/min. to - 5 °C/min.
• Tg glass transition temperature
• the present invention which comprises preheat treatment followed by post heat treatment, can provide a curl reduction only by a heat treatment for about 20 minutes. Accordingly, if the polyester base is heat-treated during travel so that heat shrinkage is completed, it can be rendered free of unevenness even wound in the form of roll.
• This heat treatment may be effected in a heat treatment zone disposed at the rear end of the film-forming machine or a drying zone in the undercoating procedure.
• a polyester support may be generally subjected to heat treatment called heat fixing at the end of the film-forming procedure.
• heat fixing the polyester support is heated to a temperature near 200 °C.
• the material may be once cooled to a predetermined temperature by cold air or cooling drum, and then passed through a heat treatment zone having a predetermined temperature gradient to effect the heat treatment of the present invention.
• This heat treatment may be effected by means of an infrared heater, high temperature steam, etc.
• this heat treatment be effected at a coating procedure such as the coating of undercoating layer and back layer. This is because that such a coating procedure has a long drying zone that can be also used by the heat treatment process of the present invention, resulting in a reduction in the facility investment.
• the thickness of the support is preferably from 60 ⁇ m to 122 ⁇ m.
• a hygroscopic gelatin layer is generally coated on the support to a thickness of 3 to 30 ⁇ m. When dried, this gelatin layer shrinks, producing a great shrinkage stress that causes the film to be deformed in the form of gutter. This gutter-shaped curl deteriorates the flatness required upon picture taking and printing and reduces the passability of the film.
• a support is required which is elastic high enough to withstand the shrinkage stress.
• 122 ⁇ m is a thickness that can be accomplished with TAC and is out of the reduction in the thickness of the support, which is one of the objects of the present invention. Accordingly, the thickness of the support is preferably from 60 ⁇ m to 122 ⁇ m.
• An ultraviolet absorbent may be incorporated in these polymer films for the purpose of providing age stability.
• an ultraviolet absorbent a compound which exhibits no absorption in the visible range is preferred.
• the amount of such an ultraviolet absorbent to be incorporated is normally in the range of 0.5 % by weight to 20 % by weight, preferably 1 % by weight to 10 % by weight based on the weight of the polymer film. If it falls below 0.5 % by weight, the effect of inhibiting the ultraviolet deterioration cannot be expected.
• an ultraviolet absorbent examples include benzophenone ultraviolet absorbents such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octhoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, benzotriazole ultraviolet absorbents such as 2(2'-hydroxy-5-methylphenyl)benzotriazole, 2(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole and 2(2'-hydroxy-3'-di-t-butyl-5'-methylphenyl)benzotriazole, and salicylic ultraviolet absorbents such as phenyl salicylate and methyl salicylate.
• benzophenone ultraviolet absorbents such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenz
• the refraction index of a polyester, particularly aromatic polyester, is as high as 1.6 to 1.7.
• the refraction index of gelatin, which is a main component of the light-sensitive layer to be coated on the polyester support is from 1.50 to 1.55, which is smaller than that of the polyester. Accordingly, rays which are incident upon the film edge is reflected by the interface of the base with the emulsion layer, causing a so-called light-piping (edge fogging).
• the color tone is preferably gray from the standpoint of general properties of photographic materials. Further, a dye having an excellent heat resistance in the film-forming temperature of polyester film and an excellent compatibility with polyester is preferred.
• the polyester film of the present invention can be provided with slipperiness depending on the application.
• an inactive inorganic compound may be incorporated in the polyester film or a surface active agent may be coated on the polyester film as an ordinary method.
• inactive inorganic grains there may be exemplified grains of SiO2, TiO2, BaSO4, CaCO3, talc, kaolin, etc.
• inactive inorganic grains there may be exemplified grains of SiO2, TiO2, BaSO4, CaCO3, talc, kaolin, etc.
• the provision of slipperiness with internal grains by allowing a catalyst or the like which has been incorporated in the system during the polymerization reaction of polyester to deposit may be used.
• external grains there may be used SiO2 grains, which exhibit a refraction index relatively close to that of polyester film.
• internal grains which can be deposited in relatively small grain diameters may be preferably used.
• layers provided with a function may be preferably laminated to provide a higher film transparency.
• coextrusion method by a plurality of extruders, feed blocks or multi manifold dies.
• the most suitable antistatic agent (or electrically conductive material) to be used in the present invention comprises finely divided grains of one crystallizable metal oxide selected from the group consisting of ZnO, TiO2, SnO2, Al2O3, In2O3, SiO2, MgO, BaO, MoO3 and V2O5 or composite thereof.
• Particularly preferred among these materials is an electrically conductive material comprising SnO2 as a main component and antimony oxide in an amount of about 5 to 20 % and/or other components (e.g., silicon oxide, boron, phosphur).
• These finely divided grains of electrically conductive crystallizable oxides or composite thereof exhibit a volume resistivity of 107 ⁇ cm or less, more preferably 105 ⁇ cm or less.
• the grain size of these finely divided grains is preferably in the range of 0.002 to 0.7 ⁇ m, particularly 0.005 to 0.3 ⁇ m.
• Such an electrically conductive layer containing the electrically conductive material may be on the silver halide emulsion layer side or on the back layer side of the support opposite the silver halide emulsion layer.
• the binder to be incorporated in the electrically conductive layer is not specifically limited and may be a water-soluble or organic-soluble binder or may be crosslinked as in latex.
• the volume resistivity of the antistatic layer thus obtained is in the range of 103 ⁇ to 1012 ⁇ , more preferably 103 to 1010 ⁇ , further preferably 103 ⁇ to 109 ⁇ .
• the silver halide photographic material of the present invention may comprise a magnetic recording layer to record various data.
• ferromagnetic materials there may be used known compounds.
• the magnetic recording layer is preferably provided on the back side of the support.
• the magnetic recording layer may be provided by coating or printing.
• the photographic light-sensitive material may be provided with a space for optical recording.
• the silver halide emulsion layer may be for color or black-and-white photographic materials. The description will be made hereinafter with reference to color silver halide photographic materials.
• the present photographic material can comprise at least one blue-sensitive layer, at least one green-sesitive layer and at least one red-sensitive layer on a support.
• the number of silver halide emulsion layers and light-insensitive layers and the order of arrangement of these layers are not specifically limited.
• the present silver halide photographic material comprises light-sensitive layers consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity and different light sensitivities on a support.
• the light-sensitive layers are unit light-sensitive layers having a color sensitivity to any of blue light, green light and red light.
• these unit light-sensitive layers are normally arranged in the order of red-sensitive layer, green-sensitive layer and blue-sensitive layer as viewed from the support. However, the order of arrangement can be optionally reversed depending on the purpose of application. Alternatively, two unit light-sensitive layers having the same color sensitivity can be arranged with a unit light-sensitive layer having a different color sensitivity interposed therebetween.
• Light-insensitive layers such as various interlayers can be provided between these silver halide light-sensitive layers and on the uppermost layer and lowermost layer.
• interlayers can comprise couplers, DIR compounds or the like as described in JP-A-61-43748, 59-113438, 59-113440, 61-20037 and 61-20038. These interlayers can further comprise a color stain inhibitor as commonly used.
• the plurality of silver halide emulsion layers constituting each unit light-sensitive layer are disclosed in West German Patent 1,121,470, British Patent 923,045, JP-A-57-112751, 62-200350, 62-206541, 62-206543, 56-25738, 62-63936, and 59-202464, and JP-B-55-34932, and 49-15495 (The term "JP-B” as used herein means an "examined Japanese patent publication").
• Silver halide grains may be so-called regular grains having a regular crystal form, such as cube, octahedron and tetradecahedron, or those having an irregular crystal form such as sphere and tablet, those having a crystal defect such as twinning plane, or those having a combination of these crystal forms.
• the silver halide grains may be either fine grains of about 0.2 ⁇ m or smaller in diameter or giant grains having a projected area diameter or up to about 10 ⁇ m.
• the emulsion may be either a monodisperse emulsion or a polydisperse emulsion.
• the preparation of the silver halide photographic emulsion which can be used in the present invention can be accomplished by any suitable method as described in Research Disclosure No. 17643 (December 1978), pp. 22 - 23, "I. Emulsion Preparation and Types", and No. 18716 (November 1979), page 648, Glafkides, "Chimie et Physique Photographique", Paul Montel (1967), G. F. Duffin, "Photographic Emulsion Chemistry", Focal Press, 1966, and V. L. Zelikman et al., “Making and Coating Photographic Emulsion Focal Press", 1964.
• Tablet grains having an aspect ratio of about 5 or more can be used in the present invention.
• the preparation of such tablet grains can be easily accomplished by any suitable method as described in Gutoff, "Photographic Science and Engineering", vol. 14, pp. 248 - 257, 1970, U.S. Patents 4,434,226, 4,414,310, 4,433,048, and 4,439,520, and British Patent 2,112,157.
• the individual silver halide crystals may have either a homogeneous structure or a heterogeneous structure composed of a core and an outer shell differing in halogen composition, or may have a layered structure. Furthermore, the grains may have fused thereto a silver halide having a different halogen composition or a compound other than silver halide, e.g., silver thiocyanate, lead oxide, etc. by an epitaxial junction.
• the silver halide emulsion to be used in the present invention is normally subjected to physical ripening, chemical ripening and spectral sensitization. Additives to be used in these steps are described in Research Disclosure Nos. 17643 and 18716 as tabulated below.
• Dye image stabilizer p.25 9. Hardening agent p. 26 p.651 LC 10. Binder p. 26 p.651 LC 11. Plasticizer and lubricant p. 27 p. 650 RC 12. Coating aid and surface active agent pp. 26-27 p.650 RC
• the photographic material to be processed in the present invention can comprise various color couplers. Specific examples of the color couplers are described in the patents described in the above cited Research Disclosure No. 17643, VII-C to G.
• Preferred yellow couplers include those described in U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752, 4,248,961, 3,973,968, 4,314,023, and 4,511,649, JP-B-58-10739, British Patents 1,425,020 and 1,476,760, and European Patent 249,473A.
• Preferred magenta couplers include 5-pyrazolone compounds and pyrazoloazole compounds. Particularly preferred are those described in U.S. Patents 4,310,619, 4,351,897, 3,061,432, 3,725,067, 4,500,630, 4,540,654, and 4,556,630, European Patent 73,636, JP-A-60-33552, 60-43659, 61-72238, 60-35730, 55-118034, and 60-185951, RD Nos. 24220 (June 1984) and 24230 (June 1984), and WO88/04795.
• Cyan couplers include naphthol and phenol couplers. Preferred are those described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, 4,327,173, 3,446,622, 4,333,999, 4,753,871, 4,451,559, 4,427,767, 4,690,889, 4,254,212, and 4,296,199, West German Patent Disclosure No. 3,329,729, European Patents 121,365A and 249,453A, and JP-A-61-42658.
• Colored couplers for correction of unnecessary absorptions of the developed dye preferably include those described in Research Disclosure No. 17643, VII-G, U.S. Patents 4,163,670, 4,004,929, and 4,138,258, JP-B-57-39413, and British Patent 1,146,368.
• Couplers which form a dye having moderate diffusibility preferably include those described in U.S. Patent 4,366,237, British Patent 2,125,570, European Patent 96,570, and West German Patent Publication No. 3,234,533.
• DIR couplers which release a development inhibitor are described in the patents cited in RD 17643, VII-F, JP-A-57-151944, 57-154234, 60-184248, and 63-37346, and U.S. Patents 4,248,962.
• Couplers capable of imagewise releasing a nucleating agent or a developing accelerator at the time of development preferably include those described in British Patents 2,097,140 and 2,131,188, and JP-A-59-157638 and 59-170840.
• the photographic material according to the present invention can further comprise competing couplers as described in U.S. Patent 4,130,427, polyequivalent couplers as described in U.S. Patents 4,283,472, 4,338,393, and 4,310,618, DIR redox compounds releasing couplers, DIR couplers releasing couplers, DIR coupler-releasing redox compounds, or DIR redox releasing redox compounds as described in JP-A-60-185950 and 62-24252, couplers capable of releasing a dye which returns to its original color after release as described in European Patents 173,302A, bleach accelerator-releasing couplers as disclosed in RD Nos.
• competing couplers as described in U.S. Patent 4,130,427, polyequivalent couplers as described in U.S. Patents 4,283,472, 4,338,393, and 4,310,618, DIR redox compounds releasing couplers, DIR couplers releasing couplers, DIR coupler-releasing redox compounds
• the incorporation of the couplers of the present invention in the light-sensitive material can be accomplished by any suitable known dispersion method.
• high boiling organic solvents having a boiling point of 175 °C or higher at normal pressure include phthalic esters, phosphoric or phosphonic esters, benzoic esters, amides, alcohols or phenols, aliphatic carboxylic esters, aniline derivatives, and hydrocarbons.
• auxiliary solvent there can be used an organic solvent having a boiling point of about 30 °C or higher, preferably 50 °C to about 160 °C.
• Typical examples of such an organic solvent include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.
• the total thickness of all hydrophilic colloidal layers on the emulsion side is preferably in the range of 28 ⁇ m or less.
• the film swelling T 1/2 is preferably in the range of 30 seconds or less, more preferably 20 seconds or less.
• the film thickness is determined after being stored at a temperature of 25 °C and a relative humidity of 55 % for 2 days.
• the film swelling T 1/2 can be determined by a method known in the art, e.g., by means of a swellometer of the type as described in A. Green et al., "Photographic Science and Engineering", vol. 19, No. 2, pp. 124-129.
• T 1/2 is defined as the time taken until half the saturated film thickness is reached wherein the saturated film thickness is 90 % of the maximum swollen film thickness reached when the photographic material is processed with a color developer at a temperature of 30 °C over 195 seconds.
• the film swelling T 1/2 can be adjusted by adding a film hardener to gelatin as binder or altering the ageing condition after coating.
• the percentage swelling of the photographic material is preferably in the range of 150 to 400 %.
• the percentage swelling can be calculated from the maximum swollen film thickness determined as described above in accordance with the equation: (maximum swollen film thickness - film thickness)/film thickness.
• the color photographic material according to the present invention can be developed in accordance with an ordinary method as described in RD Nos. 17643 (pp. 28 - 29), and 18716 (left column - right column on page 651).
• the silver halide color photographic material of the present invention may contain a color developing agent for the purpose of simplifying and expediting processing.
• a color developing agent is preferably used in the form of various precursors. Examples of such precursors include indoaniline compounds as described in U.S. Patent 3,342,597, Schiff's base type compounds as described in U.S. Patent 3,342,599, and Research Disclosure Nos. 14,850 and 15,159, and compounds as described in Research Disclosure No. 13,924.
• the film specimen was cut into a 1.2 m long and 35-mm wide strip. The specimen was then allowed to stand at a temperature of 25 °C and a relative humidity of 60 % over night. The specimen was then wound around a spool having a diameter of 4 to 12 mm with its light-sensitive layer inside. The specimen was enclosed in a container, and then heated to a temperature of 80 °C for 2 hours to get curl. This temperature condition is based on the supposition that the film is left inside a car in the summerseason.
• the film thus curled was then allowed to cool in a 25 °C room over night.
• the film specimen was withdrawn from the sealed container, processed in an automatic processor (Minilabo FP-560B, available from Fuji Photo Film Co., Ltd.).
• the development conditions are set forth below.
• the specimen used for measurement was processed with a processing solution which had been used for running processing of a specimen which had been imagewise exposed until the color developer was replenished three times the tank capacity.
• Processing step Temperature Time Color development 38 °C 3 min. Bleach 38 °C 2 min. Fixing 38 °C 3 min. Rinsing 38 °C 3 min. Stabilization 38 °C 0.5 min.
• the various processing solutions used had the following compositions: Color developer Caustic soda 2 g Sodium sulfite 2 g Potassium bromide 0.4 g Sodium chloride 1 g Borax 4 g Hydroxylamine sulfate 2 g Disodium ethylenediaminetetraacetate dihydrate 2 g 4-Amino-3-methyl-N-ethyl-N-( ⁇ -hydroxyethyl) aniline monosulfate 4 g Water to make 1 l Bleaching solution Ferric (III) sodium ethylenediamine-tetraacetate dihydrate 100 g Potassium bromide 50 g Ammonium nitrate 50 g Boric acid 5 g Aqueous ammonia to adjust pH to 5.0 Water to make 1 l Fixing solution Sodium thiosulfate 150 g Sodium sulfite 15 g Borax 12 g Glacial acetic acid 15 ml Potassium alum 20 g Water to make 1 l Stabilizing bath Boric acid
• the curling degree of the film specimen is measured by test method A of ANSI/ASC PH1.29-1985 and is represented as 1/R (m) (in which R indicates the radius of the curl) by means of a curling plate at a temperature of 25°C and a relative humidity of 60 %.
• the film specimen After processed in an automatic processor (Minilabo FP-560B), the film specimen are visually evaluated as follows.
• the criterion of evaluation of unevenness is based on the following three degreees: E: It is uniformly processed. F: Unevenness is slightly observed on the processed film but no unevenness is observed on the image printed therefrom, that is, it has no problem for practical use. P: Unevenness is observed not only on the processed film but also on the image printed therefrom.
• the film specimen After processed in an automatic processor (Minilabo FP-560B), the film specimen are visually evaluated as follows.
• the criterion of evaluation of unevenness is based on the following three degreees: E: No break F: Some breaks are present but do not obstruct the conveying on printing, resulting in a normal print image. p: Breaks are present such that they obstruct the conveying on printing.
• the specimen on which a light-sensitive layer had been coated was cut into a 35-mm wide and 1.2-m long strip. The specimen was then allowed to stand at a temperature of 25 °C and a relative humidity of 10 % over night. The specimen was put on a flat table with the light-sensitive layer downward. The height of the specimen was measured by means of a vernier caliper.
• Table 5-2 of Example 3 with Reference B as a reference type, those showing a greater value than that of Reference B were evaluated poor (P) while those showing the same or smaller value than that of Reference B were evaluated excellent (E).
• the specimen coated with up to a light-sensitive layer was cut into a 35-mm wide and 1.2-m long strip.
• the specimen was wound around the spool having a diameter indicated in Table 5-2, allowed to stand for 30 minutes, developed in accordance with the foregoing development method, and then visually evaluated for fogging. Those showing fogging were evaluated poor (P) while those showing no fogging were evaluated excellent (E).
• the specimen is cut on the emulsion side and back side with a razor in such a manner that 6 lines run 5 mm apart from each other horizontally and vertically to make 25 squares.
• An adhesive tape (Nitto Tape, available from Nitto Electric Industry Co., Ltd.) is then put on the surface of the specimen. The adhesive tape is quickly peeled off at an angle of 180 degree.
• a grade those having an area left unpeeled in a proportion of 95 % or more are considered B grade, those having an area left unpeeled in a proportion of 90 % or more are considered C grade, those having an area left unpeeled in a proportion of 60 % or more are considered D grade, and those having an area left unpeeled in a proportion of less than 60 % or more are considered E grade.
• the adhesive strength grades which are practical enough for photographic materials are A and B grades.
• the film specimen is scratched and marked X on the emulsion layer side and back layer side with a steel pen in the processing solution at the various processing stages, i.e., color development, fixing and stabilization.
• the film specimen is then vigorously rubbed with a rubber-sheathed finger five times.
• the maximum width of the areas peeled along the line of X mark is determined.
• a grade those showing areas on the emulsion layer and back layer peeled to an extent less than the scratch are considered A grade, those showing a maximum peel width of 2 mm or more are considered B grade, those showing a maximum peel width of 5 mm or less are considered C grade, and those showing a maximum peel width of more than 5 mm are considered D grade.
• the adhesive strength grade which is practical enough for photographic materials is A grade.
• the specimen which has not been exposed is allowed to stand at a temperature of 25 °C and a relative humidity of 10 % for 6 hours.
• the specimen is rubbed with a rubber roller and an urethane roller in a darkroom under the same air conditions, processed in an automatic processor (Minilabo FP-560B) and then examined for static mark.
• the criterion of evaluation of static mark is based on the following four degrees:
• the film specimen (20 cm x 20 cm) which has been undeveloped and the film specimen (20 cm x 20 cm) which has been developed are vigorously rubbed with nylon at a temperature of 25 °C and a relative humidity of 10 %, and then examined for attraction of tobacco ash.
• the criterion of evaluation is based on the following four degrees:
• PET chips and PEN chips were each melt-extruded.
• the material was then lengthwise oriented by a factor of 3.4 and crosswise oriented by a factor of 4 to prepare a 80- ⁇ m thick biaxially-oriented polyester film.
• the lengthwise orientation zone had an infrared radiation heater installed as an auxiliary heating source on one side (side to be brought into contact with the casting drum upon casting, hereinafter referred to as "CD side").
• PEN was treated at an extrusion temperature of 300 °C, a lengthwise orientation temperature (CD side) of 140 °C, a crosswise orientation temperature of 130 °C and a heat fixing temperature of 250 °C (6 seconds).
• PET was treated at an extrusion temperature of 270 °C, a lengthwise orientation temperature (CD side) of 100 °C, a crosswise orientation temperature of 110 °C and a heat fixing temperature of 220 °C (6 seconds).
• the film thus formed tends to be curled with its low temperature side inside.
• the films obtained by the above mentioned method were each subjected to heat treatment under the conditions as set forth in Table 1.
• the heat treatment was effected on the film wound around a 30-cm diameter core with its undercoating side outside.
• Specimens A-1 and B-1 were prepared free from heat treatment.
• Supports A-1 to A-5, A-7 and B-1 to B-3 were each subjected to glow discharge treatment on both sides thereof under a reduced pressure of 0.2 mm Hg at an output of 2,500 W and an intensity of 0.5 KV ⁇ A ⁇ min/m2.
• Specimen A-6 which had been formed from PEN in the same manner as above, extruded at a temperature of 300 °C, lengthwise oriented at a temperature of 140 °C (CD side) and crosswise oriented at a temperature of 130 °C, and then heat-fixed at a temperature of 250 °C for 6 seconds, was free from glow discharge treatment.
• Polyoxyethylenenonylphenyl ether (polymerization degree: 10) 0.1 part by weight Water 2.2 parts by weight Methanol 95.35 parts by weight
• Back layers having the following composition were coated on the side of the undercoated supports opposite the undercoating layer.
• stannic chloride hydrate and 23 parts by weight of antimony trichloride were dissolved in 3,000 parts by weight of ethanol to make a uniform solution.
• a 1 N sodium hydroxide solution was added dropwise to the solution until the pH value of the solution reached 3 to obtain a coprecipitate of colloidal stannic oxide and antimony oxide.
• the coprecipitate thus obtained was then allowed to stand at a temperature of 50 °C for 24 hours to obtain a reddish-brown colloidal precipitate.
• the average grain diameter of the grains was 0.05 ⁇ m.
• the reddish-brown colloidal precipitate was then subjected to centrifugal separation.
• the precipitate thus separated was then washed with water by centrifugal separation to remove excess ions. This procedure was repeated three times to remove excess ions.
• a mixture of 40 parts by weight of the fine powder and 60 parts by weight of water was adjusted to a pH value of 7.0.
• the solution was then roughly dispersed by an agitator.
• the solution was then dispersed by a horizontal sand mill (Dinomill available from Willy A. Backfen AG) until the residence time reached 30 minutes.
• the dispersion exhibited an average grain diameter of 0.15 ⁇ m as calculated in terms of secondary particle agglomerate.
• a layer having the following composition was coated on the support to a dry thickness of 0.2 ⁇ m.
• the material was then dried at a temperature of 115 °C for 30 seconds. (It was confirmed that the inner temperature of the casing and the substantial temperature of the conveying roller in the conveying system had been 115 °C.)
• Dispersion of finely divided electrically conductive grains SnO2/Sb2O3; 0.10 ⁇ m) 10 parts by weight Gelatin 1 part by weight Water 27 parts by weight Methanol 60 parts by weight Resorcinol 2 parts by weight Polyoxyethylenenonylphenyl ether (polymerization degree: 10) 0.01 parts by weight
• a back layer dispersion having the following composition was prepared with diacetyl cellulose as a binder.
• Silicon dioxide (average grain diameter: 0.3 ⁇ m) 0.01 parts by weight
• Aluminum oxide 0.03 parts by weight
• Diacetyl cellulose 1.0 part by weight Methyl ethyl ketone 9.4 parts by weight
• Cyclohexanone 9.4 parts by weight
• Polyoxyethyleneparanonylphenol ether (polymerization degree: 10) 0.06 parts by weight Trimethylolpropane/3-toluenediisocyanate adduct 0.03 parts by weight
• Colloidal silica (aerogel, average grain diameter: 0.02 ⁇ m) 0.02 parts by weight C8F17SO2N(CH3)(CH2CH2O)6H 0.01 parts by weight
• Poly(vinylidene bifluoride/vinylidene tetrafluoride) (molar ratio: 9 : 1) 0.01 parts by weight Poly(methyl methacrylate/div
• the dispersion was effected at 2,000 rpm for 2 hours by means of a sand grinder.
• the two following lubricants were mixed in a proportion of 4 : 1. To the mixture was then added xylene in the same amount. The material was then dissolved at an elevated temperature of 100 °C. To the solution was added isopropanol at room temperature at a time in an amount 10 times that of the lubricant solution under stirring with ultrasonic vibration applied thereto to obtain a dispersion. The dispersion was then dilluted with a 70/25/5 (by weight) mixture of xylene, cyclohexanone and isopropanol. The solution was then subjected to fine dispersion by a high pressure homogenizer (25 °C, 300 kg/cm2) to provide a lubricant concentration of 0.1 % by weight.
• a high pressure homogenizer 25 °C, 300 kg/cm2
• the coating was effected by a slide coating method to a thickness of 15 mg/m2.
• the material was then dried at a temperature of 115 °C for 5 minutes. (It was confirmed that the inner temperature of the casing and the substantial temperature of the conveying roller in the conveying system had been 115 °C.)
• n-C17H35COOC30H61-n 4 parts by weight n-C30H61O(CH2CH2O)10H 1 part by weight
• the main materials to be incorporated in the various layers are classified as follows:
• Specimens A-1 and B-1 which have been prepared from PEN and PET, respectively, free from heat treatment, exhibits a relatively high degree of curl.
• Specimens A-2 and A-4 which have been heat-treated at a temperature of from 50 °C to lower than Tg of PEN, exhibits a sifficiently low degree of curl while Specimens A-3 and A-5, which have been heat-treated at a temperature of higher than Tg of PEN or lower than 50 °C, exhibits a relatively high degree of curl and thus cannot enjoy the heat treatment effect of the present invention.
• Specimen B-2 which has been heat treated at a temperature of 50 °C, enjoys some of the heat treatment effect on curl.
• Specimen B-3 which has ben heat treated at a temperature of 80 °C, which is an expected internal temperature of car in the summerseason, shows no reduction of curl.
• the supports which have been subjected to glow discharge treatment exhibit an excellent adhesion on both the emulsion layer and back layer.
• the specimens of the present invention comprising an electrically conductive layer exhibits excellent anstatic properties after development while Specimen A-7, which has been formed free of such an electrically conductive layer, exhibits poor antistatic properties.
• Pellets of PEN, PET, PAr, PCT, and polyester copolymers shown in Table 4 were each previously dried at a temperature of 150 °C for 4 hours. These materials were extruded through a biaxial kneading extruder at a temperature of 280 °C singly or in mixing proportions as set forth in Table 4, and then pelletized. To 100 parts by weight of the polyesters were each then added a dye Diaresin (available from Mitsubishi Chemical Industries Ltd.) in such an amount that the polyester film having a thickness of 85 ⁇ m exhibits an absorbance of 0.05 at 400 nm. The materials were each then dried by an ordinary method.
• the materials were each molten at a temperature of 300 °C, extruded through a T-die, lengthwise oriented at a temperature of Tg + 30 °C by a factor of 3.3, crosswise oriented at a temperature of Tg + 20 °C by a factor of 3.3, and then heat-fixed at a temperature of 250 °C for 6 seconds to obtain films having thicknesses as shown in Table 4 as References 1 to 23.
• a glow discharge treatment was effected in the same manner as in Example 1 except that the temperature shortly before the passage of the film by the electrodes was 115 °C.
• a corona discharge treatment was effected as follows. A 30-cm wide support was treated by means of 6KVA model of solid-state corona treatment machine available from Pillar for 20 m/min. With the reading of current and voltage, the object was treated at 0.375 KV ⁇ A ⁇ min/m2. The discharge frequency during treatment was 9.6 KHz. The gap clearance between the electrode and the dielectric roll was 1.6 mm.
• the base was subjected to glow discharge treatment or corona discharge treatment, wound in the form of roll with a tension of 70 g applied per a width of 1 cm, and then allowed to stand for 1 day.
• the specimen was then evaluated for blocking resistance. Those showing no blocking were evaluated as excellent (E) while those showing blocking were evaluated as poor (P).
• the undercoating layer, emulsion layer and back layer were provided in the same manner as in Example 1.
• the photographic films thus prepared were each wound around a spool having an outer diameter of 11 mm and then evaulated for rear end break upon development and adhesion in the same manner as in Example 1.
• References 1, 6, 13, 15 and 18 of the present invention which have been prepared from a glow discharged polyester support having a glass transition temperature of 90 °C to 200 °C, exhibit an excellent adhesion while References 2, 7, 14, 16 and 19, which have been prepared from the same polyester support free from glow discharge treatment, exhibit a poor adhesion.
• Reference 8 which has been prepared from a polyester support having a glass transition temperature of not higher than 90 °C, exhibits an excellent adhesion but shows a deteriorated blocking resistance of base after discharge treatment and a significant film rear end break upon development.
• Reference 12 exhibits a reduced blocking resistance of base after discharge treatment and a significant film rear end break upon development.
• Supports A-1 to A-17, and B to G were prepared as follows: Support A: To 100 parts by weight of a commercially available polyethylene-2,6-naphthalate polymer was added a dye Diaresin (available from Mitsubishi Chemical Industries Ltd.) in such an amount that the film having a thickness of 80 ⁇ m exhibits an absorbance of 0.05 at 400 nm. The material was then dried by an ordinary method.
• a dye Diaresin available from Mitsubishi Chemical Industries Ltd.
• the material was molten at a temperature of 300 °C, extruded through a T-die, lengthwise oriented at a temperature of 140 °C by a factor of 3.3, crosswise oriented at a temperature of 130 °C by a factor of 3.3, and then heat-fixed at a temperature of 250 °C for 6 seconds to obtain films having thicknesses of 55 ⁇ m, 60 ⁇ m and 80 ⁇ m.
• Support B A commercially available polyethylene terephthalate polymer was biaxially oriented by an appropriate method to obtain a film having a thickness of 90 ⁇ m.
• Supports C, D, E, F, G The concentration of the dye to be incorporated was the same as that in Supports A.
• the materials were each dried, molten at a temperature of 300 °C, extruded through a T-die, lengthwise oriented at a temperature of Tg + 30 °C by a factor of 3.3, crosswise oriented at a temperature of Tg + 20 °C by a-factor of 3.3, and then heat-fixed at a temperature of 250 °C for 6 seconds to obtain films having thicknesses as set forth in Table 5-1.
• Supports A-1 to A-17 and B to G thus prepared were then subjected to preheat treatment and post heat treatment under the conditions as set forth in Table 5-1, followed by the surface treatment as mentioned below.
• the H2O partial pressure in the atmospheric gas for glow discharge treatment and the film preheating temperature were controlled as set forth in Table 5-1.
• the pressure in the vacuum tank and the discharge frequency, voltage and intensity were the same as used in Example 1.
• Photographic film specimens A-1 to A-17, and B to G thus prepared were evaluated for curl, gutter-shaped curl, pressure marking, dry and wet adhesion, static mark and dustproofing properties.

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• 1993
  • 1993-08-19 DE DE1993628144 patent/DE69328144T2/de not_active Expired - Fee Related
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