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
  • G03C1/93—Macromolecular substances therefor
• • 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

Definitions

• ABSTRACT The present invention is directed to the use of polypropylene supports for photographic materials.
• the support contains 15 to 35% by weight of talc, 3 to 15% by weight of titanium white and 0.1 to 5% by weight of a fatty acid metal salt.
• a baryta paper which has generally been used as a support for light-sensitive silver halide photographic printing material, is undesirably high in water absorption despite of its being excellent in whiteness, opacity, rigidity, etc. Accordingly, a silver halide photographic material using the baryta paper as support has such disadvantages that when subjected to photographic treatment, the photographic material not only consumes large quantities of developing, fixing, bleaching and the like processing solutions and hence is required to be subjected to water-washing over a long period of time, but also gives a print which is inferior in gloss and smoothness of its surface so that the print cannot be made sufficient in gloss and smoothness unless there is adopted such specific finishing step as ferrotype drying.
• a so-called polyethylene laminate paper prepared by applying onto both sides of a paper a thin film composed mainly of a polyethylene, for example, is used as the support for silver halide photographic material.
• the polyethylene laminate paper is low in rigidity and hence has such disadvantage that it should be made great in thickness so as to be made high in rigidity required for a printing material. Since the polyethylene laminate paper is lower in water absorption than the baryta paper, the amounts of processing solutions consumed in the photographic treatment of a photographic material using the polyethylene laminate paper as support are smaller and the period of time required for water-washing of the photographic material may be made shorter.
• the processing solutions penetrate into the paper, which is the intermediary substrate of the laminate, through its cross-section. Accordingly, when the said photographic material is subjected to rapid processing, wherein the water-washing treatment is conducted only for a short period of time, there is brought about such disadvantage that stains are formed at the peripheral portion of the print due to residual processing solutions which have penetrated into the intermediary paper substrate through its crosssection. Even when there is not adopted such finishing step as ferrotype drying, the photographic material using the polyethylene laminate paper can give a print which is higher in gloss and smoothness than in the case where the baryta paper is used.
• the surface of the polyethylene layer is not sufficient in smoothness due to the arrangement of pulp fibers of the paper, and thus it is still impossible to say that the resulting print is sufficient in gloss.
• the polyethylene laminate paper due to its laminate structure, has such disadvantage that the procedure for preparation of the laminate paper itself is quite uneconomical due to the increased number of steps.
• the object of the present invention is to provide a support for lightsensitive photographic printing material which is free from the above-mentioned disadvantages.
• Another object of the invention is to provide a lightsensitive silver halide photographic printing material having a silver halide emulsion layer which has been firmly adhered to the above-mentioned support.
• the said object can be accomplished by using as the support a polypropylene sheet comprising a main resin component of a polypropylene having a melt flow index (hereinafter abbreviated to MFI) of 5 to 100, 15 to 35% by weight of talc, 3 to 15% by weight of titanium white, and 0.1 to 5% by weight of a fatty acid metal salt.
• MFI melt flow index
• a silver halide emulsion layer is formed on the said support, a compound having at least two ethyleneimino groups in one molecule and, in combination therewith, at least one water-dispersible particulate high molecular substance composed of a homopolymer of ethyl acrylate or butyl acrylate, or a copolymer of at least one of ethyl acrylate and butyl acrylate with vinylidene chloride into a gelatin-containin g layer which is in contact with said support, i.e.
• a polypropylene sheet is made white and opaque by incorporation of a white pigment such as titanium white or the like, in general. By mere incorporation of such white pigment, however, the polypropylene sheet cannot be made higher in rigidity. In case the polypropylene sheet is desired to be enhanced also in rigidity, therefore, fine powdery talc should additionally be incorporated therein.
• a polypropylene sheet incorporated with titanium white and talc is additionally incorporated with a fatty acid metal salt, whereby the polypropylene sheet, when used as the support of a lightsensitive photographic material, can be made free from such disadvantages derived from talc as mentioned above.
• the polypropylene used as the main resin component of the polypropylene sheet according to the present invention is a homopolymer of propylene or a copolymer comprising a major proportion of propylene and a minor proportion of ethylene or other a-olefin, and has an MFI of 5 to 100.
• MFI molecular fraction
• a polypropylene having an MFI of less than 5 it is rather difficult to obtain a print which is sufficient in gloss. This tendency is particularly marked when the amount of talc incorporated is large.
• the resulting sheet is undesirably embrittled to a great extent.
• the homopolymer of propylene is most preferred.
• the propylene homopolymer as compared with a propylene copolymer has a greater rigidity and this serves to prevent curling caused by the dimensional change of a photographic emulsion layer due to temperature variation.
• the homopolymer has a higher heat deformation temperature than the copolymer, and because of this, use of the homopolymer enables to employ high temperature drying with avoiding the possible deformation of selvedge portions of film strips during any drying step for photographic preparation and handling. This means considerable economical advantages such as time saving and simplified drying apparatus.
• the propylene homopolymer which has a higher solidification temperature than the propylene copolymer allows to shorten a cooling time required for shaping and consequently makes the shaping of poly propylene support more speedy.
• the homopolymer is free from any undesired high molecular weight polymeric mass which is sometimes observed in the block copolymer of propylene as the result of homopolymerization of its comonomer, and so it can make sure more uniform dispersion of talc, pigment, etc., therein.
• any other suitable resin component may be used, if necessary, in such a small amount as not to injure the effect of the present invention.
• Suitable as such additional resin component are included polyethylenes, the randam copolymers of polypropylene with ethylene or other a-olefins, polyisobutylenes, etc.
• Incorporation of 3 to 20% of an ethylene-propylene rubber or a polyisobutylene into the propylene homopolymer is particularly advantageous because it improves brittleness of said homopolymer without sacrifying desirable rigidity, high heat deformation temperature, high solidification temperature, etc., which are inherent to the propylene homopolymer.
• Talc is markedly effective for enhancing the rigidity of a polypropylene sheet and is also useful for increasing the opacity thereof, but sometimes decreases the whiteness and gloss.
• the amount of the said talc to be added is to 35% by weight based on the weight of the polypropylene sheet. In case the amount of the tale is less than 15% by weight, the polypropylene sheet is insufficient in rigidity, while in case the amount thereof is more than 35% by weight, the sheet becomes too brittle to be put into practical use.
• titanium white is particularly excellent in hiding power and hence is preferably used in the present invention.
• the amount of titanium white to be added is 3 to 15% by weight based on the weight of the polypropylene sheet.
• the sheet becomes sufficient in opacity and whiteness.
• the amount of titanium white is less than 3% by weight, the sheet is insufficient in opacity, while the addition of titanium white in such an amount as more than 15% by weight is not only uneconomical but also becomes a cause for embrittlement of the sheet.
• the average particle size of titanium white is ordinarily less than 1 micron. When such titanium white is used, the sheet is not decreased in gloss.
• titanium white is classified into rutileand anatase-type crystal structures.
• titanium white of any crystal structure may be used.
• titanium white of the anatase type structure is preferably used, since it shows a brighter whiteness.
• the fatty acid metal salt used in the present invention not only inhibits the formation of fog derived from talc as mentioned previously, but also serves to enhance the polypropylene sheet in whiteness and gloss.
• the amount of the fatty acid metal salt to be added is preferably 0.1 to 5% by weight based on the weight of the polypropylene sheet. In case the amount of the fatty acid metal salt is less than 0.1% by weight, the formation of fog cannot sufficiently be inhibited, while in case the amount thereof is more than 5% by weight, the metal salt exduates out on the surface of the polypropylene sheet, and, due to its releasing effect, the sheet is deteriorated in adhesion to silver halide emulsion layer or sub layer and tends to cause peeling of film.
• fatty acid metal salt there may effectively be used a metal salt of a saturated or unsaturated fatty acid having 8 to 22 carbon atoms which can be easily obtained commercially.
• Typical examples of such metal salt are salts of lithium, magnesium, calcium, zinc, aluminum and the like metals of stearic, palmitic and oleic acids.
• the polypropylene sheet according to the present invention may be incorporated with, in addition to such talc, titanium white and fatty acid metal salt as mentioned previously, any of such other additives as, for example, stabilizers, particularly phenolic stabilizers, antistatic agents, auxiliary fillers and pigments, brighteners, plasticizers, etc., in such proper amounts as not to injure the effect of the present invention.
• additives for example, stabilizers, particularly phenolic stabilizers, antistatic agents, auxiliary fillers and pigments, brighteners, plasticizers, etc.
• a conventional process for preparing a polypropylene sheet may be utilized as it is.
• a resin composition comprising the aforesaid components which has been melted and kneaded by use of an extruder is extruded through a T-die and then subjected to a chill-roll, so that one side of the resulting sheet comes to have a mirror surface, or if necessary a rough surface having a controlled roughness, e.g. a reticular surface such as silk surface, and the other side of the sheet comes to have a surface which has been so roughened as to be writable.
• a silver halide emulsion is coated on the polypropylene sheet prepared according to the abovementioned process and is then dried, whereby a light-sensitive silver halide photographic material can be obtained.
• the coating of the silver halide emulsion on the polypropyl ene sheet may be carried out in the same manner as in the case of a polyethylene laminate paper. That is, the surface of the polypropylene sheet is previously subjected to corona discharge treatment, flame treatment or oxidize treatment to enhance the adhesion thereof to silver halide emulsion layer, and then the silver halide emulsion is directly coated on the sheet surface.
• the polypropylene sheet is subjected to subbing treatment to form a sub layer thereon, and then the silver halide emulsion is coated on the sub layer.
• a light-ser.sitive silver halide photographic printing material free from peeling of coating can be obtained.
• the silver halide emulsion layer should have been adhered particularly firmly to the support.
• a compound having at least two ethyleneimino groups in one Continued molecule and, in combination therewith, at least one water-dispersible particulate high molecular substance (11') El 3 composed of a homopolymer of ethyl acrylate or butyl acrylate, or a copolymer of at least one of ethyl acrylate 5 and butyl acrylate with vinylidene chloride, are incor-
• the above-mentioned compound is known as a hardener for such colloid as gelatin, caseine or gum carabic, and is sometimes incorporated into a silver halide emulsion.
• the silver halide emulsion layer is not so enhanced in adhesion to the support, i.e. the polypropylene sheet of the present invention.
• the silver halide emulsion layer is greatly enhanced in adhesion to the support.
• the water-dispersible particulate high molecular substance used in the present invention is a plastic substance having an average particle size of less than about 0.5 micron which is composed of a homopolymer of ethyl acrylate or butyl acrylate, or a copolymer of at least one of ethyl acrylate and butyl acrylate with vinylidene chloride.
• the said high molecular substance can easily be prepared according to emulsion polymerization using such anion activator as sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium aryl polyethylene glycol ether sulfonate or sodium alkyl polyethylene glycol ether sulfonate as emulsifier, and alkali persulfate, ammonium persulfate or hydrogen peroxide as polymerization initiator.
• the molecular weight of the high molecular substance is preferably about 10,000 to 1,000,000.
• the ratio of acrylate to vinylidene chloride is preferably from :90 to 90:10.
• the thus obtained substance had an activator content of 1.7%, a specific gravity (di of 1.051 and an average particle size of 0.1 micron, and a 1% dispersion of said substance had a transmission of 73.2%.
• At least one of such substance as synthesized in the above-mentioned manner is incorporated, either as it is or in the form of an aqueous dispersion, into a gelatin-containing subbing solution or into a silver halide emulsion when the emulsion is to be directly coated on the support, i.e. the polypropylene sheet of the present invention.
• the said substance may be incorporated at any stage during preparation of the subbing solution or the silver halide emulsion, and the amount thereof is preferably about 5 to 60% by weight based on the weight of the gelatin in said solution or emulsion.
• the silver halide emulsion layer is not so enhanced in adhesion to the polypropylene sheet of the present invention.
• the silver halide emulsion layer is greatly enhanced in adhesion to the polypropylene sheet.
• water-dispersible particulate high molecular substances as, for example, polyvinyl acetate, polyvinylidene chloride, styrenebutadiene copolymer, vinyl acetate-ethylene copolymer, acrylonitrile-butadiene copolymer and vinyl acetate-acrylate copolymer.
• polyvinyl acetate polyvinylidene chloride
• styrenebutadiene copolymer vinyl acetate-ethylene copolymer
• acrylonitrile-butadiene copolymer and vinyl acetate-acrylate copolymer.
• the amount of the compound having at least two ethyleneimino groups in one molecule which is used in the present invention varies depending on the kind of the layer into which the compound is to be incorporated, the kind of the silver halide emulsion used, and the kind and amount of the water-dispersible particulate high molecular substance used in combination with said compound. Generally, a sufficient effect can be obtained when the amount of said compound is 0.1 to 10% by weight based on the amount of gelatin in the layer, into which the compound is to be incorporated.
• the said compound is, of course, not limited to be used in such amount as mentioned above, but may be used in an optional amount so far as the effect of the present invention can be obtained.
• the compound may be added at any stage during preparation of the subbing solution or silver halide emulsion used to form a sub layer or silver halide emulsion layer, but is preferably added immediately before coating of the solution or emulsion.
• the silver halide emulsion applicable to the support of the present invention may contain any of such silver halides as silver bromide, silver chloride and silver iodide, and mixtures thereof such assilver chlorobromide, silver iodobromide, etc., and may be any of the high and low speed type emulsions.
• the silver halide emulsion may be subjected to chemical sensitization such as sulfur-, reductionor gold-sensitization, or to optical sensitization using a sensitizing dye, and may be incorporated with any of various photographic additives such as stabilizers, antifoggants, ultraviolet absorbers, coating aids, etc.
• the silver halide emulsion may be incorporated with couplers for forming a colored image by color development.
• couplers for forming a colored image by color development.
• the light-sensitive silver halide photographic material using as.the support the polypropylene sheet according to thepresent invention is particularly useful for contact printing or enlargement printing. When a high speed silver halide emulsion is used, however, the photographic material may be used for direct photographing by use of a special camera.
• a support for light-sensitive silver halide photographic material which is markedly excellent in whiteness, opacity, rigidity, gloss, smoothness and nonwater absorption.
• a lightsensitive silver halide photographic material using the support according to the present invention consumes smaller amounts of developing, fixing bleaching and the like processing solutions and is extremely shorter in period of time required for water-washing treatment.
• the photographic material can give a print markedly excellent in gloss and smoothness.
• Y1 ASTM D-1925-63T (The smaller the Y1 value, the lower the yellowness and the higher the whiteness.)
• Fog density JIS K-7611-60 EXAMPLE 1
• a mixture comprising 68.9% by weight of a powdery polypropylene having an MP1 of 7.0, 0.1% by weight of 2,6-di-tert-butyl p-cresol (hereinafter abbreviated to BHT) as an antioxidant, 15.0% by weight of fine powdery talc having an average particle size of 2.0 microns, 15.0% by weight of rutile type titanium white having an average particle size of 0.3 micron, and 1.0% by weight of any of such fatty acid metal salts as shown in Table 1 was sufficiently kneaded by means of a Henschel mixer, extruded by use of an extruder at 200C., and then cut to the form of grains.
• BHT 2,6-di-tert-butyl p-cresol
• the grains were shaped at a melt temperature of 250C. to prepare a sheet having a thickness of 250 microns.
• sheet Nos. 1 to 10 were prepared by varying the kind of the fatty acid metal salt. The surface of each sheet was subjected to corona discharge treatment so that the contact angle of water became 60. Subsequently, an ordinary silver chlorobromoiodide emulsion for printing paper was coated on the treated surface of each sheet and then dried to obtain printing papers Nos. 1a to 10a.
• a sheet No. 11 was prepared in the same manner as above, except that the fatty acid metal salt was not used and the powdery polypropylene wasused in an amount of 69.9% by weight, and then treated in the same manner as above to obtain a printing paper No. 1121.
• the printing paper No. lla using as the support the sheet No. l l which was not incorporated with fatty acid metal salt is extremely high in fog density
• the printing paper Nos. la to 10a using as the supports the sheet Nos. 1 to 10, which were incorporated with the fatty acid metal salts are low in fog density and thus are marked in fog-inhibiting effect due to incorporation of the fatty acid metal salts into the sheets used as the supports.
• the printing papers Nos. la to 10a according to the present invention were subjected to ordinary exposure and development, and then dried in hot air without the use of ferrotype to obtain prints which were markedly excellent in gloss.
• EXAMPLE 2 A powdery polypropylene having an MP1 of 7.0, BHT as an antioxidant, fine talc powder having an average particle size of 1.5 microns, anatase-type titanium white having an average particle size of 0.3 micron, and zincstearate were blended together in such proportions (%by weight) as shown in Table 2 to form compositions of the prescriptions 1 to 4.
• the compositions were individually shaped in the same manner as in Example 1 to prepare sheet Nos. 14 to 17. After subjecting the surface of each sheet to corona discharge treatment, the same silver halide emulsion for printing as in Example l was coated on the treated surfaces of the sheets and then dried to obtain printing paper Nos. 14a to 17a.
• the printing paper Nos. 14a to 16a according to the present invention were subject to ordinary exposure and development, and then dried in hot air without the use of ferrotype to obtain prints which were markedly excellent in gloss.
• the samples were individually incubated at 50C. and 80 RH for 24 hours and at 25C. and 60% RH for 1 week, and then subjected to development. During the development and after drying, the samples were measured in adhesion of the emulsion layer to the polypropylene sheet to obtain such results as shown in Table 4.
• the film of each sample during the development was scribed with a knife so as to form a checkered pattern, and then strongly rubbed with hand to observe whether the coating was peeled or not.
• the film of each sample after drying was scribed with a knife so as to form a checkered pattern, and an adhesive tape was firmly adhered to the film and then rapidly stripped to observe whether the film was peeled or not.
• A The pattern was not peeled at all B: The corner of the pattern was slightly peeled.
• samples Nos. 20 to 29 were prepared by varying the kind and proportion of the water-dispersible high molecular substance and those of the hardener.
• Example 5 The samples were individually incubated under the same conditions as in Example 3, and then subjected to development. During the development and after drying, the samples were measured in adhesion of the emulsion layer to the polypropylene sheet in the same manner as in Example 3 to obtain such results as shown in Table 5.
• weight of gelatin in the emulsion, and the amount of the A polypropylene Support as claimed in claim 1 hardener is represented by ml. of a 2% aqueous soluwherein Said polypropylene is the homopolymer of tion of the hardener. 5 propylene From Table It is "l that only.the i k 3.
• a polypropylene support as claimed in claim 1, where said support is subbed with a subbing composition comprising a hardener compound having at least two ethyleneimino groups in its molecule and a waterdispersible, particulate high molecular substance which is the copolymer of ethyl acrylate or butyl acrylate with Polyethyl acrylate as a water-dispersible high molecular substance and the previously exemplified compound (18) as a hardener were mixed together in such proportions as shown in Table 6, and the resulting mixture was added to 1 kg. of a subbing solution comprising a 4% aqueous gelatin solution. Subsequently, the subbing solution was coated on the polypropylene 2O sheet No.
• the Samples were incubated under the 7. A light..sensitive ilver photographic matesame conditions as in Exampl and then Subjected to rial which comprises at least one silver halide emulsion development.
• a polypropylene Sheet i ing the samples were measured in adhesion of the i a m i r si component ofapolypropylene h i emulsion layer to the polypropylene sheet in the same a melt flow index of 5 to 100, 15 to by weight of manner as in Example 3 to obtain such results as shown talc, 3 to 15% by weight of titanium white, and 0.1 to
• a polypropylene support for photographic use comprising a main resin component of a polypropylene, together with 15 to 35% by weight of talc, 3 to 15% by weight of titanium white, and 0.1 to 5% by weight of a fatty acid metal salt, all the weight percents graphic material.
• a polypropylene support as claimed in claim 4 which bears thereon a light-sensitive silver halide photographic emulsion to form a light-sensitive photographic material.

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• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Laminated Bodies (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 1974
  • 1974-01-28 GB GB384674A patent/GB1447710A/en not_active Expired
  • 1974-01-28 US US437244A patent/US3888679A/en not_active Expired - Lifetime
  • 1974-01-28 IT IT67227/74A patent/IT1014046B/it active
  • 1974-01-29 DE DE2404162A patent/DE2404162C2/de not_active Expired

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