EP0672942A2 - Verfahren zur Herstellung von photographischem Druckpapier oder photographischem Film - Google Patents

Verfahren zur Herstellung von photographischem Druckpapier oder photographischem Film Download PDF

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Publication number
EP0672942A2
EP0672942A2 EP95103997A EP95103997A EP0672942A2 EP 0672942 A2 EP0672942 A2 EP 0672942A2 EP 95103997 A EP95103997 A EP 95103997A EP 95103997 A EP95103997 A EP 95103997A EP 0672942 A2 EP0672942 A2 EP 0672942A2
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EP
European Patent Office
Prior art keywords
manufacturing
photosensitive material
paper
acid
resin
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95103997A
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English (en)
French (fr)
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EP0672942A3 (de
Inventor
Kunihiko C/O Fuji Film Co. Ltd Kikuchi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0672942A2 publication Critical patent/EP0672942A2/de
Publication of EP0672942A3 publication Critical patent/EP0672942A3/de
Withdrawn legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—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
    • G03C1/00—Photosensitive materials
    • G03C1/74—Applying photosensitive compositions to the base; Drying processes 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
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
    • 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

  • the present invention relates to a method of manufacturing photographic printing papers or photographic films and, more particularly, to a method of continuously manufacturing photographic printing papers or photographic films without requiring any winding processes.
  • photographic films In analogy with photographic printing papers, photographic films also have so far been manufactured through independently arranged processes, although the manufacture of photographic films starts from a high molecular resin film instead of the laminated paper prepared going through the processes from (1) to (5).
  • a first object of the present invention is to provide a method of manufacturing photographic printing papers or photographic films which enables a very considerable reduction in large stock space which conventional manufacturing processes require.
  • a second object of the present invention is to provide a method of manufacturing photographic printing papers or photographic films which enables a diminution in products loss, including a stock loss and a loss in the roll-core part.
  • a method of manufacturing a photosensitive material which consists mainly of a substrate having emulsion layers via a subbing layer on one side and a backing layer on the other side, wherein the photosensitive material is a photographic printing paper or a photographic film and at least two processes comprising the process of applying a subbing layer to the substrate on the side for the emulsion layers and the process subsequent thereto in which the backing layer is applied on the reverse side of the substrate are performed continuously.
  • Fig. 1 is a flow chart which illustrates the processes constituting a conventional manufacturing method (See Comparative Example 1).
  • Fig. 2 is a flow chart which illustrates the processes constituting a manufacturing method according to the present invention (See Example 1).
  • Fig. 3 is a flow chart which illustrates the processes constituting another manufacturing method according to the present invention (See Example 2).
  • the present invention has no particular restriction as to a substrate, and so there can be used as the substrate a raw paper made mainly from natural pulp, a raw paper made from a mixture containing natural pulp and synthetic fibers or synthetic pulp in an arbitrary ratio, a paper laminated with a waterproof resin on both sides, films or plates of plastics such as polycarbonate, polystyrene, polyacrylate, polymethacrylate, polyethylene terephthalate (PET), etc., metal plates and so on.
  • the substrates particularly preferred in the present invention are base papers disclosed, e.g., in JP-A-04-69648 (the term "JP-A" as used herein means an "unexamined published Japanese patent application").
  • wood kraft pulp such as soft wood kraft pulp, hardwood kraft pulp or soft wood-hardwood mixture kraft pulp
  • wood kraft pulp such as soft wood kraft pulp, hardwood kraft pulp or soft wood-hardwood mixture kraft pulp
  • these types of pulp may be prepared using any of the cooking methods, namely polysulfide cooking, batch cooking and continuous cooling methods, or they may be prepared so as to have a proper hardness or Kappa number.
  • they may be prepared by the oxygen pulping method disclosed in JP-B-59-38575 (the term "JP-B" as used herein means an "examined Japanese patent publication").
  • the wood kraft pulp used herein is prepared by the following process: Wood chips are cooked with a muddy liquor containing sodium hydroxide and sodium sulfide as chemical components, and lignin is removed therefrom. Thereafter, in the presence of a defoamer or a foam inhibitor, the resulting matter is separated into pulp fibers and the cooking residue (black liquor), washed and then subjected to a bleaching treatment.
  • the muddy liquor used therein for cooking may additionally contain cooking aids such as salts including sodium carbonate, sodium sulfate, calcium hydroxide, calcium carbonate and the like, sodium borohydride, anthraquinone compounds and so on.
  • natural pulp is suitable.
  • wood sulfide pulp such as soft wood sulfide pulp, hardwood sulfide pulp or soft wood-hardwood mixture sulfide pulp is preferred.
  • wood soda pulp and wood dissolving pulp may be used.
  • the defoamer or foam inhibitor used in the bleaching treatment of pulp can be properly chosen from known ones.
  • the chemicals containing as the deforming or foam-inhibiting component a higher fatty acid alcohol ester compound, a mineral oil or liquid hydrocarbon oil, a silicone oil or the like, as disclosed in JP-A-54-59404, JP-A-58-220896, JP-A-61-245391, JP-A-61-245319, U.S. Patent 3,923,638 and U.S. Patent 4,107,073, may be used.
  • a water-base or oil-base defoamer or foam inhibitor containing a mineral oil or a liquid hydrocarbon oil as a main component is preferred over the others with respect to the defoaming or foam-inhibiting power.
  • the defoamer or foam inhibitor used herein may contain additional ingredients such as hydrophobic silica, an ethylenebis(higher alkyl amide), a silicone oil and so on.
  • additional ingredients such as hydrophobic silica, an ethylenebis(higher alkyl amide), a silicone oil and so on.
  • hypochlorite bleaching For chlorine bleaching in the natural pulp preparation, chlorine gas or chlorine water is used. Therein, chlorine dioxide may be used together.
  • sodium hydroxide For alkali treatment or extraction, sodium hydroxide is used to advantage, but calcium hydroxide, ammonia or a mixture thereof may be used.
  • hypochlorite bleaching a bleaching powder obtained by making chlorine act on powdery solid of calcium hydroxide or, from an industrial point of view, hypochlorite bleaching liquor prepared by blowing chlorine gas into milk of lime or a dilute sodium hydroxide solution (the so-called calcium-hypo bleaching liquor or sodium-hypo bleaching liquor) is suitable.
  • chloride dioxide prepared by a sulfite process, such as Mathieson process, new Mathieson process, Managero method, C.I.P. process, etc., or a hydrochloric acid process such as casting process, Nissoh process, Solvay process, etc.
  • peroxides used for peroxide bleaching under an alkaline condition there can be suitably used inorganic and organic peroxides such as hydrogen peroxide, sodium peroxide, peroxide bleaching liquor (an aqueous mixture containing hydrogen peroxide, sodium hydroxide and sodium silicate, and optionally magnesium sulfate) peracetic acid, 1-butylhydroperoxide and mixtures of two or more thereof.
  • Suitable examples of an alkali used therein include hydroxides of alkali and alkaline earth metals, such as sodium hydroxide, aqueous ammonia, magnesium hydroxide, calcium hydroxide and mixtures of two or more thereof.
  • the bleaching can be carried out under a condition properly chosen from those described, e.g., in a book entitled “Pulp shori oyobi Hyohaku” (which means “Treatments and Bleaching of Pulp”) compiled by Kami Pulp Gijutsu Kyokai (published in January 27, 1968) and JP-B-58-43732.
  • a proper combination of additives which can be chosen from among a sizing agent such as a metal salt of fatty acid and/or a fatty acid, the alkylketene dimer emulsion or the epoxidized higher fatty acid amide disclosed in JP-B-62-7534, alkenyl- or alkylsuccinic acid anhydride emulsions, rosin derivatives, etc.; a dry paper strength reinforcer such as anionic, cationic or amphoteric polyacrylamides, polyvinyl alcohol, cationized starch (as disclosed, e.g., in JP-A-03-171042), vegetable galactomannan, etc.; a wet paper strength reinforcer such as polyaminepolyamide-epichlorohydrin resins, etc.; a filler such as clay, kaoline, calcium carbonate, titanium oxide, etc.; a fixing agent such as water-soluble aluminum salts
  • additives including various water-soluble polymers and antistatic agents can be incorporated in the paper stock by means of a spray or a tub size press.
  • the starch polymers disclosed in JP-A-01-266537 are examples thereof.
  • the antistatic agents which can be used are electrically conductive substances, including nonionic surfactants represented by polyoxyethylene glycols, anionic surfactants, cationic surfactants represented by quaternary ammonium salts, amphoteric surfactants, alkylamine derivatives, fatty acid derivatives, various lubricants, carbon black, graphite, metal-coated pigments, metallic powders, metallic flake, carbon fibers, metallic fibers, whiskers (potassium titanate, alumina nitride, alumina) and so on.
  • alkali metal salts such as sodium chloride, potassium chloride, etc,; alkaline earth metal salts such as calcium chloride, barium chloride, etc.; colloidal metal oxides such as colloidal silica, etc.; and organic antistatic agents such as polystyrenesulfonates, etc.
  • the latexes and emulsions which can be added petroleum resin emulsions and latexes of a styrene-acrylic acid-acrylate copolymer, a styrene-acrylic acid-butadiene copolymer, an ethylene-vinyl acetate copolymer, a styrene-maleic acid-acrylate copolymer and the like are examples thereof.
  • the pigments which can be added clay, kaoline, talc, barium sulfate and titanium oxide are examples thereof.
  • the pH modifiers which can be added hydrochloric acid, phosphoric acid, citric acid and sodium hydroxide are examples thereof. It is desirable for these additives to be added together with other additives properly chosen from the above-cited ones, including colored pigments, colored dyes, brightening agents and so on.
  • the raw paper which is prepared by making paper from a paper stock containing an epoxidized fatty acid amide and having the pH adjusted to 5.5-6.5, controlling the water content in the paper to 1-4 % by weight and then subjecting the paper to a surface sizing treatment with an alkaline aqueous solution to control the paper surface pH to 7-8.
  • the surface of a substrate be so smooth as to have Bekk smoothness of at least 100 seconds when measured according to JIS P8119.
  • a substrate having surface smoothness of at least 200 seconds is favored.
  • the substrate having Bekk smoothness of at least 100 seconds can be prepared generally by using a pulp containing a large proportion of hardwood pulp, which has a tendency to easily make a smooth surface, and beating the pulp with a beater so that the long fibers therein may have the lowest possible content.
  • the paper stock slurry to which internal additives have been added is made into paper having uniform formation by means of a generally used paper machine, such as a Fourdrinier paper machine, a cylinder paper machine or so on.
  • the paper obtained is further subjected to a calender treatment with a machine calender, a super calender, a hot calender or the like.
  • a calender treatment with a machine calender, a super calender, a hot calender or the like.
  • the raw paper used in the present invention has no particular restriction as to the thickness. However, it is desirable for the raw paper to have a basis weight ranging from 40 g/m2 to 250 g/m2 .
  • the printing thereon may be performed using any of general printing methods, such as gravure printing, flexographic printing, letterpress printing, offset printing, etc.
  • this printing process may be carried out after the raw paper was once wound into a roll, and that before the covering the raw paper with a waterproof resin layer, it is preferable in view of the reduction in stock space and stock loss that this optional printing process be carried out without inserting a winding process after the papermaking process and be succeeded by the next process so as to be a continuous operation.
  • the raw paper is covered with a waterproof resin layer on both sides.
  • the covering is carried out by lamination process firstly on the reverse side where the application of emulsions is not intended, and then on the front side to which photographic emulsions are to be applied.
  • the waterproof resin contain fine grains of titanium dioxide and optionally a bluing agent.
  • the covering layer may be a single layer or may be constituted of two or more layers. In the latter case, it is preferable to laminate all the constituent layers simultaneously from the viewpoint of the reduction in process number.
  • polyolefins such as polyethylene, polypropylene and ethylene copolymers are suitable examples thereof.
  • polyethylene is used to advantage.
  • the polyethylene used herein may be high-density polyethylene, low-density polyethylene, linear low-density polyethylene or a mixture thereof.
  • MFR melt flow rate
  • MFR of a polyolefin resin in an unprocessed state is intended to include MFR of the resin into which neither a bluing agent nor titanium dioxide has not yet been kneaded and MFR of the resin which has not yet been mixed with any resins for dilution.
  • the bluing agent known pigments such as ultramarine blue, cobalt blue, cobalt phosphate oxide, quinacridone pigments and mixtures of two or more thereof can be contained in the waterproof resin layer.
  • the grain size of a bluing agent has no particular limitation. In general, commercially available bluing agents have a grain size of the order of 0.3 ⁇ 10 ⁇ m. So far as the bluing agent has its grain size in such a range, it is well fit for use. Additionally, different bluing agents may be used in the upper and the lower layers respectively.
  • the content of a bluing agent in the topmost layer be in the range of 0.01 to 0.8 % by weight, preferably 0.05 to 0.6 % by weight, and particularly preferably 0.1 to 0.4 % by weight, and the content in layers disposed on the lower side be in the range of 0 to 0.6 % by weight, preferably 0.01 to 0.45 % by weight, and particularly preferably 0.05 to 0.3 % by weight.
  • the bluing agent is kneaded into a waterproof resin with a kneading machine such as a two-rod roll mill, a three-rod roll mill, a kneader, a Bumbury's mixer or the like, and molded in the form of pellets, which are used as a master batch.
  • a kneading machine such as a two-rod roll mill, a three-rod roll mill, a kneader, a Bumbury's mixer or the like.
  • the concentration of the bluing agent in the pellets ranges from 1 to 30 % by weight.
  • both anatase-type and rutile-type TiO2 may be used.
  • anatase-type TiO2 when priority is given to the achievement of high whiteness; while rutile-type TiO2 is preferable when priority is given to the achievement of high sharpness.
  • a blend of anatase-type TiO2 and rutile-type TiO2 may be used, or the TiO2-containing layer may be constituted of the upper layer in which which anatase-type TiO2 is used and the lower layer in which rutile-type TiO2 is used.
  • the upper and the lower layers may be the same or different in TiO2 concentration, and the TiO2 concentrations therein can be arbitrarily chosen from the range of 5 to 20 % by weight.
  • TiO2 Prior to the incorporation into the waterproof resin layer, TiO2 is generally subjected to a surface treatment for the purpose of depressing its activity to inhibit the yellowing phenomenon.
  • Suitable examples of an agent which can be used for such a surface treatment include inorganic materials such as hydrated aluminium oxide, hydrated silicon oxide, etc. and organic materials such as a polyhydric alcohol, a polyamine, a metal soap, an alkyl titanate, a polysiloxane, etc. It is desirable that such a surface treatment agent as cited above be used in a proportion of from 0.2 to 2.0 % by weight to TiO2 when it is an inorganic material, while when it is an organic material it be used in a proportion of from 0.1 to 1.0 % by weight to TiO2. Further, it is desirable for the TiO2 used to have an average grain size of the order of 0.1 to 0.4 ⁇ m.
  • TiO2 also can be kneaded into the waterproof resin.
  • a low molecular weight waterproof resin a metal salt of higher fatty acid, an ester of higher fatty acid, a higher fatty acid amide, a higher fatty acid or so on can be used therein as dispersing aid.
  • TiO2 is kneaded into a waterproof resin by means of a kneading machine, such as a two-rod roll, a three-rod roll, a kneader, a Bumbury's mixer or the like, wherein a metal salt of higher fatty acid, an ethyl ester of higher fatty acid, a higher fatty acid amide, a higher fatty acid or so on is further used as dispersing aid.
  • a kneading machine such as a two-rod roll, a three-rod roll, a kneader, a Bumbury's mixer or the like, wherein a metal salt of higher fatty acid, an ethyl ester of higher fatty acid, a higher fatty acid amide, a higher fatty acid or so on is further used as dispersing aid.
  • the TiO2 concentration in the thus prepared pellets is in the range of about 30 to about 75 %.
  • At least the resin layer which covers the raw paper on the side where emulsion layers are to be applied can contain at least one kind of additive chosen from among known antioxidants, lubricants, surfactants, etc.
  • antioxidants for the purpose of preventing the resin from undergoing oxidative decomposition to produce an aldehyde or a ketone which causes the generation of fog and abnormal sensitivity in a photographic film, or from the standpoint of preventing the generation of non-soluble foreign matter and coloration troubles. Representatives of such antioxidants are described below.
  • 6-t-Butyl-3-methylphenol derivatives 2,6-di-t-butyl-p-cresol, t-butylphenol, 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-butylidenebis(6-t-butyl-m-cresol), 4,4'-thiobis(6-t-butyl-m-cresol), 4,4'-dihydroxydiphenylcyclohexane, alkylated bisphenols, styrene-introduced phenols, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(3',5'-di-t-butyl-4'-hydrpoxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis
  • 6-Ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,4-trimethyl-1, 2-dihydroquinone polymers and trimethyldihydroquinoline derivatives are examples thereof.
  • Phenyl- ⁇ -naphthylamine, N-phenyl- ⁇ -naphthylamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di- ⁇ -naphthyl-p-phenylenediamine and N-(3'-hydroxybutylidene)-1-naphthylamine are examples thereof.
  • 2-Mercaptobenzimidazole, zinc salt of 2-mercaptobenzoimidazole and 2-mercaptomethylimidazole are examples thereof.
  • Alkylated-aryl phosphites diphenylisodecyl phosphite, tris(nonylphenyl)phosphite ⁇ sodium phosphite, and triphenyl phosphite are examples thereof.
  • Thiourea derivatives such as 1,3-bis(dimethylaminopropyl)-2-thiourea are examples thereof.
  • Dilauryl thiodipropionate is an example thereof.
  • the phenol type antioxidants are preferred over the others. Especially, the antioxidants of hindered phenol type are effective.
  • antioxidants of hindered phenol type commercial products, e.g., Irganox series produced by Ciba Geigy Co., Ltd. and Sumilizer series, BHT, BH-76, WX-R and BP-101, produced by Simitomo Chemical Co., Ltd. can be used to advantage.
  • an antioxidant chosen from the group consisting of 2,6-di-t-butyl-p-cresol (BHT), the antioxidants of low volatile high-molecular phenol type (those having the trade names, Irganox 1010, Irganox 1076, Topanol CA, Ionox 330, etc.), dilauryl thiodipropionate, distearyl thiopropionate and dialkyl phosphates.
  • BHT 2,6-di-t-butyl-p-cresol
  • the amount of an antioxidant added (by weight) be in the range of 0 to 8,000 ppm, preferably 20 to 3,000 ppm and particularly preferably 50 to 1,500 ppm.
  • the antioxidant When the antioxidant is added in an amount greater than 8,000 ppm, it produces bad influences upon photosensitive materials, including photographic films and photographic printing papers, because oxidation-reduction reactions are utilized therein. Specifically, excess addition of antioxidants sometime causes abnormality in photographic properties andtends to deteriorate the adhesiveness of the resin layer to a substrate. Therefore, it is desired that the antioxidant be added in the smallest possible amount so far as it can prevent the troubles of coloration and adhesion and the generation of lamps.
  • Dimelthylpolysiloxanes of various grades, modified products thereof and a wide variety of modified products of other silicones (represented by siloxanes) are included therein.
  • carboxyl-modified silicones As typical examples thereof, mention may be made of carboxyl-modified silicones, ⁇ -methylstyrene-modified silicones, ⁇ -oleic acid-modified silicones, polyether-modified silicones, fluorine-modified silicones, specially modified hydrophilic silicones, olefin polyether-modified silicones, epoxy-modified silicones, amide-modified silicones, alcohol-modified silicones, alkyl-modified silicones, alkylaryl-modified silicones, amino-modified silicones and alkyl- and hydrogen-modified silicones (produced by Shin-Etsu Silicone Co., Ltd. and Toshiba Silicone Co., Ltd.).
  • silicones of various types is desirable because they not only have improving effects upon the resin's flowability and lubricity, but also can achieve unexpected effects if a light-shielding material and a coloring material are added together therewith. Specifically, they can have elevating effects upon the dispersibilities of light-shielding and coloring materials, the coloring power of coloring material, and so on.
  • Electrostripper TS-2 and TS-3 (trade names, the products of Kao Corporation) and so on are examples thereof.
  • Liquid paraffin, natural paraffin, micro wax, synthetic paraffin, polyethylene wax, polypropylene wax, chlorinated hydrocarbons, fluorocarbons and the like are examples thereof.
  • Lower alcohol esters of fatty acids polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, aliphatic alcohol esters of fatty acids and the like are examples thereof.
  • Polyhydric alcohols polyglycols, polyglycerols and the like are examples thereof.
  • the compounds of higher fatty acids such as lauric acid, stearic acid, ricinolic acid, naphthenic acid, oleic acid, etc., with metals such as Li, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb, etc. are examples thereof.
  • the lubricants as cited above may be used alone, or as a mixture of two or more thereof, if desired.
  • the amount of lubricants added is requested to be minimized, account being taken of the prevention of a smoking phenomenon and their influences upon photographic properties of photographic light-sensitive materials such as photographic printing papers, photographic films and so on. Therefore, the proportion of lubricants added is in the range of generally 0.001 to 5 % by weight, preferably 0.005 to 5 % by weight and particularly preferably 0.01 to 3 % by weight.
  • surfactants for the purposes of heightening the dispersibilities of inorganic pigments and other additives in resins and the prevention of electrification.
  • the surfactants used for such purposes can be chosen properly from nonionic, anionic, cationic and amphoteric surfactants well known to those skilled in the arts.
  • nonionic surfactants As typical examples of nonionic surfactants, mention may be made of polyethylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene aliphatic alcohol ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene glycerine fatty acid esters, polyoxyethylene aliphatic amines, sorbitan monofatty acid esters, fatty acid pentaerythritols, ethylene oxide adducts of alipahtic alcohols, ethylene oxide adducts of fatty acids, ethylene oxide adducts of fatty acid amines or fatty acid amides, ethylene oxide adducts of alkylphenols, ethylene oxide adducts of alkylnaphthols, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, and the nonionic antistatic agents disclosed in JP-B-63-26697 (at page 120).
  • anionic surfactants As typical examples of anionic surfactants, mention may be made of various metal salts of fatty acids, ricinoleic acid ester sulfate sodium salt, sulfated oleic acid ethylaniline, olefin sulfate salts, oleyl alcohol sulfate sodium salt, alkylsulfate salts, fatty acid ethylsulfonates, alkylsulfonates, alkylnaphthalenesulfonates, alkylbenzenesulfonates, succinic acid ester sulfonates, phosphonic acid ester salts and so on.
  • cationic surfactants As typical examples of cationic surfactants, mention may be made of primary amines, tertiary amines, quaternary ammonium salts, pyridine derivatives and so on.
  • amphoteric surfactants As typical examples of amphoteric surfactants, mention may be made of carboxylic acid derivatives, imidazoline derivatives, betaine derivatives and so on.
  • the surfactants as cited above are added in a proportion ranging from 0 to 7.0 % by weight, preferably from 0.005 to 5.0 % by weight and particularly preferably from 0.01 to 3.0 % by weight.
  • thermoplastic resins especially acid-modified polyolefin resins
  • acid-modified polyolefin resins as described above is intended to include the resins obtained by subjecting polyolefin resins to the graft-modification reaction with unsaturated carboxylic acids.
  • graft-modified polyethylene resins, graft-modified polypropylene resins and graft-modified ethylene copolymer resins are examples thereof.
  • the unsaturated carboxylic acids which can be used in the foregoing reaction include their derivatives also.
  • unsaturated carboxylic acids mention may be made of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, mesaconic acid, angelic acid, citraconic acid, crotonic acid, isocrotonic acid, nagic acid (endocis-bicyclo[2,2,1]hepto -5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethtyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, monoethyl fumarate,
  • the present invention does not have any particular restriction as to the method of grafting unsaturated carboxylic acids on polyolefins.
  • any methods for instance, the melt kneading method as disclosed in JP-B-43-27421 wherein reactants undergo the reaction in a molten condition, the method as disclosed in JP-B-44-15422 wherein reactants in a state of solution undergo the reaction, the method as disclosed in JP-B-43-18144 wherein reactants in a state of slurry undergo the reaction, the method as disclosed in JP-B-50-77493 wherein the reaction is run in a vapor phase, and so on can be adopted.
  • melt kneading method wherein an extruder is used is preferred over the others because it can be performed by simple operations, and that at a low price.
  • the proportion of unsaturated carboxylic acids used be in the range of 0.01 to 20 parts by weight, preferably 0.2 to 5 parts by weight, to 100 parts by weight of polyolefin resin as the base polymer (e.g., various types of polyethylene resins, including linear low-density polyethylenes, various types of polypropylene reins, and various ⁇ -olefin copolymer resins such as ethylene-butene-1 copolymer resin, ethylene-4-methylpentene-1 copolymer resin, etc.).
  • polyolefin resin e.g., various types of polyethylene resins, including linear low-density polyethylenes, various types of polypropylene reins, and various ⁇ -olefin copolymer resins such as ethylene-butene-1 copolymer resin, ethylene-4-methylpentene-1 copolymer resin, etc.
  • organic peroxides may be used.
  • organic peroxides which can be used include benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, ⁇ , ⁇ '-bis(t-butylperoxydiisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne, di-t-butyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxylaurate, t-butyl peroxybenzoate, 1,3-bis(t-butylperoxyisopropyl)benzene, di-t-butyl-di-peroxyphthalate, t-butyl peroxymaleate, is
  • organic peroxides may be used as combination of two or more thereof.
  • peroxides particularly preferable peroxides are those having their decomposition temperatures in the range of 170 to 200 °C, namely di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne and 1, 3-bis(t-butylperoxyisopropyl)benzene.
  • peroxides are not particularly limited in amount to be added. However, it is effective to add them in an amount of 0.005 to 5 parts by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight of polyolefin resin.
  • thermoplastic resins Representatives of commercially available acid-modified thermoplastic resins (trade names) are as follows:
  • the content of an acid-modified thermoplastic resin in the resin layer is preferably in the range of 0 to 40 % by weight, particularly 10 to 30 % by weight.
  • nucleating agent in view of improvements in crystallization speed, rigidness, transparency, suitabilities for a slitter and a guillotine cutter,mechanical strength and so on, it is desirable to incorporate a nucleating agent into at least one resin layer which covers the base paper on the side where emulsion layers are to be coated.
  • the nucleating agent both organic and inorganic nucleating agents can be used herein. Representatives thereof are described below in detail.
  • an organic nucleating agent examples include carboxylic acids, dicarboxylic acids, salts and anhydrides of those acids, aromatic sulfonic acids and their salts and esters, aromatic phosphinic acids, aromatic phosphonic acids, aromatic carboxylic acids and their aluminum salts, metal salts of aromatic phosphoric acids, alkyl alcohols containing 8 to 30 carbon atoms, condensates of polyhydric alcohols and aldehydes, and alkylamines.
  • an inorganic nucleating agent which can be used include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc., alkali metal oxides such as sodium oxide, etc., alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc., alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide, etc., alkaline earth metal oxides such as calcium oxide, etc., and so on.
  • alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.
  • alkali metal oxides such as sodium oxide, etc.
  • alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc.
  • alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide, etc.
  • alkaline earth metal oxides such as calcium oxide, etc., and so on.
  • nucleating agents which can be used should not be construed as being limited to the above-cited ones, but any known nucleating agents can also be used herein. As a matter of course, those nucleating agents can be used alone or as a mixture of two or more thereof.
  • the organic nucleating agents set forth below are especially advantageous in that they have great addition effects upon improvements in acceleration of resin crystallization, suitabilities for a slitter and a guillotine cutter, rigidness, transparency (or whiteness when white pigments are contained) and so on without attended by any bad influences on a photographic light-sensitive material, such as a photographic film or a photographic printing paper.
  • dibenzylidenesorbitol compounds are preferred over the others.
  • metal salts of fatty acids to resin compositions for forming the present resin layers.
  • the purposes of diminishing a bleed-out phenomenon, preventing the organic nucleating agent from scattering and improving the dispersibility of the organic nucleating agent can also be accomplished.
  • fatty acid metal salts can bring about improvements in not only dispersibility and moldability of a light-shielding material but also photographic properties because they can neutralize halogen compounds contained in resins, which act adversely on photographic properties of a photographic light-sensitive material, to convert them to harmless compounds.
  • fatty acid metal salts include the compounds prepared from higher fatty acids, such as lauric acid, stearic acid, ricinolic acid, naphthenic acid, oleic acid, erucic acid, etc., and metals such as Li, Mg, ca, Sr, Ba, Zn, Cd, Al, Sn, Pb, etc.
  • hydrotalcite group compounds can also be used.
  • the fatty acid metal salts and/or hydrotalcite group compounds are added in a proportion of 0 to 10.0 % by weight, preferably 0.05 to 5. 0 % by weight, to 100 parts by weight of resin component.
  • the foregoing ultramarine and/or titanium dioxide-containing pellets are molten by heating, if necessary, after dilution with other heat-resisting resins, and therewith are laminated the travelling paper or synthetic paper as a raw paper using either a successive lamination method or a simultaneous multilayer lamination method utilizing a multilayer extrusion die of feed block type, multimanifold type or multislot type.
  • the lamination method adopted herein does not have any particular restriction as to the shape of multilayer extrusion die, a T-die, a coat hanger die or so on can be generally used.
  • the exit temperature of the waterproof resin lamination by hot melt extrusion is generally in the range of 280 °C to 340 °C, particularly preferably 310 °C to 330 °C.
  • activation treatments such as a corona discharge treatment, a flame treatment, a glow discharge treatment and so on.
  • the surface of the topmost waterproof resin layer on the side where emulsions are to be coated is subjected to a die embossing treatment of the type which can put thereon a gloss or the fine grain described in JP-A-55-26507 or can render the surface mat or silky.
  • the waterproof resin layer on the reverse side is subjected to a die embossing treatment of the type which makes the surface dull.
  • the process after the die embossing treatment is the same as the process of preparing photographic films using PET or cellulose ester films as base films.
  • the both-sided resin-laminated raw paper and a base film are called the substrate, hereinafter.
  • the substrate surface Prior to the application of a subbing layer and a backing layer, it is desirable for the substrate surface to undergo an activation treatment such as a corona discharge treatment, a flame treatment or so.
  • an activation treatment such as a corona discharge treatment, a flame treatment or so.
  • the base film there can be used to advantage the cellulose acetate film containing a plasticizer of phosphate type in which the content of acid impurities is less than 0.0050 mole (JP-A-06-16869) and the copolymerized polyester film which contains polyethylene terephthalate (PET) as a main component and further the metal sulfonate-containing comonomer component in a proportion of 2-7 mole % to the whole ester linkage units and additionally contains a 0.01-2.0 % by weight of antioxidant (JP-A-05-323496).
  • PET polyethylene terephthalate
  • the proportion thereof to the cellulose ester be in the range of 5 to 20 % by weight.
  • a subbing layer is provided on the resin-covered surface of the substrate on the side where photographic emulsions are to be coated, continuously from the activation treatment without winding the substrate into a roll.
  • the subbing layer is constituted of gelatin, a viscosity regulator, a surfactant, a coating aid and so on.
  • the coating composition for forming the subbing layer comprises an aqueous gelatin solution, which may optionally contain a water-soluble organic solvent, a pH regulator, a surfactant, antiseptics, a hardener, a defoamer, a white pigment, a viscosity regulator and so on.
  • any of well-known coating methods such as dip coating, air knife coating, curtain coating and roller coating methods, may be adopted.
  • a backing layer aiming at improvements in, e.g., antistatic, writing and slipping properties is provided on the resin-covered surface on the side opposite to the subbing layer.
  • the backing layer as described above is important from the viewpoints of improving writing properties and preventing a curling phenomenon, especially in the case of photographic printing paper.
  • this backing layer there can be incorporated a combination of ingredients properly chosen from the inorganic antistatic agents, the organic antistatic agents, the hydrophilic binders, the latexes, the water dispersions, the hardeners, the pigments, the surfactants and so on as disclosed, e.g., in JP-B-52-18020, JP-B-57-9059, JP-B-57-53940, JP-B-58-56859, JP-A-59-214849, JP-A-58-184144, JP-A-62-6256, JP-A-03-206440 and JP-A-04-34138.
  • the same methods as applied to the subbing layer can be used for the backing layer.
  • the silver halide emulsions used are those which have already undergone physical ripening, chemical ripening and spectrally sensitizing steps. Additives usable for these steps are described in Research Disclosure , No. 17643, No. 18716 and No. 307105. A list of the additives and the places at which they are described in those references respectively are shown below as Table 1. Table 1 Kind of Additive RD 17643 RD 18716 RD 307105 1 Chemical Sensitizer p. 23 p. 648, right column p. 866 2 Sensitivity Elevat- p.
  • two or more of light-sensitive silver halide emulsions which differ from one another in at least one characteristic, namely grain size, grain size distribution, halide composition, grain form or sensitivity, can be used as a mixture in the same layer.
  • the surface-fogged silver halide grains disclosed in U.S. Patent 4,082,553, the interior-fogged silver halide grains disclosed in U.S. Patent 4,626,498 and JP-A-59-214852, colloidal silver and the like can be desirably used for a light-sensitive silver halide emulsion layer and/or a substantially light-insensitive hydrophilic colloid layer.
  • inter-fogged or surface-fogged silver halide grains describes the silver halide grains of the kind which can be uniformly (non-imagewise) developed, whether they are present in the exposed area or the unexposed area of a photosensitive material.
  • the preparation methods of the interior- or surface-fogged silver halide grains are described in U.S. Patent 4,626,498 and JP-A-59-214852.
  • the silver halides which constitute the core part of interior-fogged silver halide grains having a core/shell structure may be the same or different in halide composition.
  • any of silver halides including silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be applied.
  • These fogged silver halide grains don't have any particular limitation on the grain size. However, it is desirable that they have an average grain size in the range of 0.01 to 0.75 ⁇ m, especially 0.05 to 0.6 ⁇ m. Also, those grains has no particular restriction as to the grain form. They may have a regular crystal form or not.
  • the emulsions prepared may be polydisperse emulsions, it is preferable for them to be monodisperse emulsions (such that at least 95 % by weight or by number of the silver halide grains have their grain sizes within ⁇ 40 % of the average grain size).
  • protective layer(s) are provided on the emulsion layers.
  • the thus obtained material is slitted and cut, thereby manufacturing finished products.
  • the present manufacturing method for photographic printing papers and photographic films has a disadvantage in that it is required of the processes embodied in a continuous through process to have the same process speed that the slowest process among them has, the advantages drawn from the present continuous through process which makes winding processes unnecessary, that is, reduction in stock space and stock loss as well as labor saving, far outweigh the disadvantage which it entails. Accordingly, the present manufacturing method is extremely useful for improving the production efficiency.
  • FIG. 1 A conventional manufacturing method (Comparative Example 1) is shown in Fig. 1, and manufacturing methods according to the present invention are shown in Fig. 2 and Fig. 3 respectively.
  • Pulp (LBKP: 100%) was beaten with a double disk refiner so as to have a freeness of 200 ⁇ 50 ml C.S.F., and then admixed with dry broke in a proportion of 20 % by weight at the most.
  • Thereto were further added as internal sizing agents 0.5 ⁇ 2.0 % by weight of polyacrylamide, 0.5 ⁇ 2.0 % by weight of sulfate band, 0.05 ⁇ 1.0 % by weight of polyamidepolyamine epichlorohydrin, 0.1 ⁇ 1 % by weight of alkylketene dimer and 0.5 % by weight of epoxidized fatty acid amide.
  • the thus obtained slurry was adjusted to pH 7 ⁇ 0.5 by the addition of sodium hydroxide, and once stored in a chest.
  • This paper stock was admixed with wet broke in a proportion of 60 % by weight at the most, and then discharged from a head box with a J/W ratio set to 0.8 ⁇ 1.2 in order to make paper.
  • the plastic wire was continued to be shaken in a shaking width of 10 ⁇ 40 mm and with the frequency of 2 ⁇ 6 Hz and, at the same time, the water was squeezed successively with a foil, a suction box, a vacuum foil box and a table roller and further the wet paper surface was conditioned by turning a dandy roll at a speed of + 1 ⁇ 5 m/min relative to the wire speed.
  • the water was further squeezed out by being nipped 2 ⁇ 6 times under the linear pressure of 20 ⁇ 100 N/mm. Thereafter, the drying operation was performed at a surface temperature of 40 ⁇ 135 °C by means of 15 ⁇ 30 drum dryers. Then, the resulting paper was nipped under linear pressure of 50 ⁇ 120 N/mm by means of a calender (1 ⁇ 3 steps), and further coated with the coating solution described below at a coverage rate of 10 ⁇ 100 cc/mm2 in the size press or gate roll coater part, followed by the drying operation at a surface temperature of 40 ⁇ 135 °C by means of 4 ⁇ 10 drum dryers.
  • the coating solution used therein was prepared by dissolving in water 0.5 ⁇ 10 % of PVA, 1 ⁇ 5 % of calcium chloride, 0.1 ⁇ 1.0 % of a brightening agent and 0.001 ⁇ 0.01 % of a fatty acid ester.
  • the resulting paper was nipped under pressure of 100 ⁇ 250 N/mm by means of a calender (1 ⁇ 4 steps) and, wound up under press pressure of 300 ⁇ 900 N/mm by means of a single drum Pope type reel. These papermaking processes were carried out at one continuous operation.
  • the thus made raw paper had a basis weight of 60 ⁇ 200 g/m2, a thickness of 60 ⁇ 200 ⁇ m and a water content of 5 ⁇ 9 %.
  • a resin mixture of a high density polyethylene (HDPE) and a low density polyethylene (LDPE) wherein a HDPE/LDPE ratio was chosen from the range of 1/9 to 9/1 was laminated on the thus printed surface using a melt-extrusion technique at a head temperature of 250 ⁇ 340 °C so as to have a coverage rate of 10 ⁇ 50 g/m2, and then die-embossed with an embossing roller through which 5 ⁇ 30°C cooling water was circulated at a flow rate of 1,000-6,000 ml/min.
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • LDPE containing 5 ⁇ 40 % by weight of TiO2 and 0 ⁇ 4 % by weight of ultramarine blue was laminated on the raw paper surface to which photographic emulsions were to be applied using a melt-extrusion technique at a head temperature of 250 ⁇ 340 °C, and then die-embossed with an embossing roller through which 5 ⁇ 30°C cooling water was circulated at a flow rate of 1,000-6,000 ml/min.
  • the thus obtained paper (web) was cooled with 1 ⁇ 3 cooling drums through which cooling water of 15 ⁇ 30°C was circulated so that the web temperature before winding might be lowered to 20 ⁇ 60°C, and then wound into a roll using a winder equipped with a press roll (linear pressure: 50 ⁇ 300 N/m).
  • Table 2 The constitution of a photographic printing paper prepared according to the foregoing processes is shown in Table 2.
  • Table 2 Raw Paper LBKP, basis weight: 180 g/m2 Resin Layer on Emulsion -coated Side LDPE, coverage rate: 35 g/m2 Resin Layer on Side opposite to Emulsion -coated Side LDPE + HDPE, coverage rate: 30 g/m2 Subbing Layer gelatin, coverage rate: 5 cc/m2 (wet) Backing Layer antistatic agent + matting agent, coverage rate: 5 cc/m2 (wet) Emulsion Layer gelatin + silver halides, thickness: 10 ⁇ m
  • Example 1 Example 2 and Comparative Example 1 were examined for the stock space required thereof, the regular loss caused by the winding operation and the days required for manufacturing photographic printing paper as the finished goods, from the preparation of paper stock till the completion of finishing. The comparison of these examination results are shown in Table 3.
  • Table 3 Stock Space Regular Loss Days for Manufacturing Finished Goods Comparative Example 1 3,000 m2 8 % 9 days Example 1 2,400 m2 4 % 6 days Example 2 1,600 m2 3 % 4 days

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Laminated Bodies (AREA)
EP95103997A 1994-03-17 1995-03-17 Verfahren zur Herstellung von photographischem Druckpapier oder photographischem Film Withdrawn EP0672942A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7382394A JPH07261322A (ja) 1994-03-17 1994-03-17 写真印画紙又は写真フィルムの製造方法
JP73823/94 1994-03-17

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EP0672942A2 true EP0672942A2 (de) 1995-09-20
EP0672942A3 EP0672942A3 (de) 1997-11-26

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014128653A1 (en) * 2013-02-25 2014-08-28 Basf Se Paper and cardboard packaging with barrier coating

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1159598A (en) * 1965-10-28 1969-07-30 Fuji Photo Film Co Ltd Multiple Coating Process and Apparatus
US5182161A (en) * 1990-07-10 1993-01-26 Mitsubishi Paper Mills Limited Support for photosensitive materials
JPH0593985A (ja) * 1991-10-02 1993-04-16 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPH05323496A (ja) * 1992-03-24 1993-12-07 Konica Corp 写真用支持体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014128653A1 (en) * 2013-02-25 2014-08-28 Basf Se Paper and cardboard packaging with barrier coating

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EP0672942A3 (de) 1997-11-26

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