Cartridge for photographic photosensitive materials

Abstract: A cartridge for photographic photosensitive materials has the internal volume of not more than 0.07 X cm³ (X is a surface area of the photosensitive layer of the photographic photosensitive material contained in it), and a cartridge body, a spool and a photographic film. The cartridge body is made of a plastic material having a sulfur content of not more than 2.5 µg/g, and made of a carbon black produced from petroleum material at more than 1300°C or produced from natural gas or vegetable oil.

Description: This invention relates to a cartridge for photographic photosensitive materials wherein the components contained in the plastic material thereof rarely deteriorate the properties of a photographic photosensitive material contained therein. In general, a cartridge for photographic photosensitive materials is composed of a cartridge body 1 in an about cylindrical shape and a spool 2 rotatably attached to the container body 1 as shown in Figure 1. A film 3 is wound on the spool 2, and extended through a slit 4 of the cartridge body 1. The cartridge body is usually made of various plastic materials, such as polypropylene resin, polystyrene resin and acrylonitrile-butadiene-styrene copolymer resin, which are blended with carbon black in order to secure light-shielding ability (FR-A-2229993). Besides, in some cartridges for photographic photosensitive materials, a spool is rotatably attached to the cartridge body, and a film wound on the spool is extended by rotating the spool (US-A-4,832,275 and US-A-4,834,306). In this type of cartridge for photographic photosenstive materials, the cartridge body is also made of the above-mentioned plastic materials. However, the above conventional cartridge for photographic photosensitive materials occasionally deteriorates the properties of the photographic photosensitive material placed therein, resulting in a useless photographic photosensitive material. Chemical Abstracts, Vol. 82, No. 16, 21st April 1975, page 509, Abstract No. 105144w discloses a combination of polyethylene stabilized with carbon black, a metallic foil and polyethylene as a 3-layer packing material for photographic paper. It is the object of the invention to provide a cartridge for photographic photosensitive materials which does not deteriorate the photographic properties of the photographic photosensitive material contained therein, particularly when it is kept at a high temperature. The inventor found that sulfur components contained in the plastic material forming the cartridge body adversely affect the photographic photosensitive materials, and further found that the sulfur components are derived from carbon black, antioxidant, rubber crosslinking agent added for improving the impact strength of polystyrenic resin, and then accomplished the invention. Thus, the present invention provides a cartridge for photographic photosensitive materials as claimed in claim 1. Figure 1 is a sectional view illustrating a partially detached state of the cartridge for photographic photosensitive materials. 1 cartridge body 2 spool 3 photographic photosensitive material 4 slit The cartridge applicable to the invention includes, for example, JIS 135 film cartridges, JIS 126 film cartridges, JIS 110 film cartridges, disk film cartridges, film magazines. In the cartridge of the invention the internal volume is not more than 0.07 X cm² wherein (X is the surface area (cm²) of the photosensitive layer of the photosensitive material contained therein. The internal volume is the void space between the inner surface of the cartridge body and the outermost surface of the photosensitive material placed in the cartridge. The cartridge can be miniaturized by rendering the internal volume not more than 0.07 X cm³. The internal volume is preferably not more than 0.06 X cm³, more preferably, not more than 0.05 X cm³. The cartridge body is composed of a plastic material having a sulfur content of not more than 2.5 µg/g, preferably not more than 2.0 µg/g. When the sulfur content is beyond 2.5 µg/g, the photographic properties are deteriorated. That is, it was found that when the amount of free sulfur components contained in carbon black is beyond about 17 ppm/g, the photographic properties are deteriorated. The carbon black is blended with the plastic material in an amount of about 15 wt. % at maximum. Therefore, when the amount of sulfur components in the cartridge body is not more than 2.5 µg/g, the photographic properties are not deteriorated. The carbon black added to the cartridge body includes carbon black produced by using natural gas or vegetable oil as the raw material such as thermal black and channel black and carbon black produced at more than 1300°C by using petroleum as the raw material. The thermal black or channel black are used as it is, because the sulfur content is very low. However, since oil furnace black, or lamp black, etc. produced by using a petroleum raw material, for example, an aromatic oil such as creosote oil, naphthalene oil, anthracene oil or heavy oil contains sulfur components, the extractable sulfur components need to be decreased by binding the sulfur components to the carbon black during the production thereof. The burning temperature is accordingly more than 1300°C and preferably the passing time through a reaction furnace is controlled to be 0.02 s. A rubber material is blended with the plastic material such as polystyrene resin in order to improve the impact strength. The rubber material has a molecular crosslinking structure in order to impart elasticity. Sulfur compounds are usable as the crosslinking agent (for example, the compounds described on pages 89 to 92 of "Separation and Analysis Techniques of Polymer Additives" published by Nihon Kagaku Gijutsu Joho). When the above sulfur compound is used as the crosslinking agent, the content of the sulfur compound is controlled so as to be not more than 2.5 µg/g. Moreover, preferable crosslinking agents used for the cartridge of the invention are described on pages 871 to 879 and pages 921 to 924 of "Plastic and Rubber Additives Manual, Enlarged Edition" published by Kagaku Kogyo-Sha. The resins usable as the plastic material include ethylene-butene-1 copolymer resin, propylene-butene-1 copolymer resin, ethylene-propylene-butene-1 ternary copolymer resin, polybutene-1 resin, styrene resin, polymethyl methacrylate resin, styrene-acrylonitrile copolymer resin, ABS resin, polypropylene resin, crystalline propylene-α-olefin copolymer resin, modified polypropylene resin, modified polyethylene resin, polypropylene-maleic acid graft copolymer resin, chlorinated polyolefin resin (mainly chlorinated polyethylene resin), ethylene ionomer resin (a resin where ethylene and an unsaturated acid is crosslinked with a metal) poly-4-methyl-pentene-1 resin, vinyl chloride-propylene copolymer resin, ethylene-vinylalchohol resin, crosslinked polyethylene resin (electron rays irradiation crosslinking, chemical corsslinking, etc.), polyisobutylene resin 1,2-polybutadiene resin, L-LDPE (linear low density polyethylene) resin, LDPE (low density polyethylene) resin, MDPE (medium density polyethylene) resin, EEA (ethylene-ethyl acrylate copolymer) resin, EVA (ethylene-vinyl acetate copolymer) resin and propylene-ethylene copolymer resin. Examples of the usable additives are described below. (1) Plasticizer; phthalic acid esters, glycol esters, fatty acid esters or phosphoric acid esters; (2) Stabilizer; lead compounds, cadmium compounds, zinc compounds, alkaline earth metal compounds or organic tin compounds; (3) Antistatic agent; cationic surractants, anionic surfactants, nonionic surfactants or ampholytic surfactants; (4) Flame retardant; phosphoric acid esters, phosphoric acid ester halides, halides, inorganic materials or polyols containing phosphor; (5) Filler; alumina, kaolin, clay, calcium caronate, mica, talc, titanium dioxide or silica; (6) Reinforcing agent; glass lobing, metallic fiber, glass fiber, glass milled fiber or carbon fiber; (7) Coloring agent; inorganic pigments (Al, Fe₂O₃, TiO₂, ZnO or CdS), organic pigments (carbon black or dyes); (8) Blowing agent; inorganic blowing agents (ammonium carbonate or sodium hydrogen carbonate), organic blowing agents (nitroso compounds or azocompounds); (9) Deterioration preventing agent; ultraviolet absorber, metal deactivator or peroxide decomposing agent; (10) Coupling agent; silane compounds, titanium compounds, chromium compounds or aluminum compounds, In the cartridge of the invention, since the sulfur content of the plastic material is not more than 2.5 µg/g, the photographic photosensitive material contained therein is rarely deteriorated by the sulfur component. The sulfur component of the plastic material is made not more than 2.5 µg/g by using a difinite amount of carbon black. EXAMPLES Example 1 The plastic material employed is composed of 68.5 wt. % of polystyrene resin, 30 wt. % butadiene-styrene copolymer resin crosslinked with 1 wt. % of diisopropylbenzenehydroperoxide and 0.5 wt. % of acetylene black (a kind of thermal black). Example 2 The plastic material employed is composed of 66 wt. % of polystyrene resin, 30 wt. % of butadiene-styrene copolymer resin crosslinked with 1 wt. % of diisopropylbenzenehydroperoxide and 3.0 wt. % of oil furnace carbon black. The furnace carbon black was made from creosote oil as the raw material at a furnace temperature of 1350°C for a passing time through the furnace of 0.02 s. Example 3 The plastic material employed is the same as in Example 2 except of using acetylene black instead of the oil furnace carbon black. Comparative Example 1 The plastic material employed is composed of 76.5 wt. % of polystyrene resin, 20 wt. % of butadiene-styrene copolymer resin crosslinked with 3 wt. % of sulfur, and 0.5 wt. % of acetylene black. Comparative Example 2 The plastic material employed is the same as in Example 2 except of using oil furnace carbon black made from creosote oil as the raw material at a furnace temperature of 1250°C for a passing time through the furnace of 0.02 s. Cartridges for photographic photosensitive materials shown in Figure 1 were molded by an injection molding machine (produced by Sumitomo Heavy Industries) at a mold clamping pressure of 150 t using the above-mentioned plastic materials. Each cartridge for photographic photosensitive materials had a weight of about 5 g. A 24 exposure film of a 135 size (produced by Fuji PHoto Film Co., Ltd., "FUJI COLOR SUPER HG 400") was loaded in each cartridge. The surface area of the photosensitive layer of the film was 403 cm², and the internal volume of the cartridge was 17.2 cm³. Each cartridge for photographic photosensitive materials wherein the film was loaded was kept at 25°C under a relative humidity of 50% for two days. Then, it was placed in a container in seal, and further kept at 60°C for three days. The color development of the film was conducted by using a development process CN-16 (indicated by Fuji Photo Film Co., Ltd.). The results are shown in the following table. Measuring method of sulfur component content; A molded article made of the plastic material was hardened by cooling with liquid nitogen and then ground, 100 g of the ground sample was placed in a Soxhlet extractor and extracted with chloroform at 60°C for 8 hours. After cooling, the whole amount of the solution was adjusted to 100 ml. 10 µl of the solution was injected into an apparatus of high speed liquid chromatography (HPLC), and the content of the sulfur component was measured quantitatively. The standard HPLC conditions were as follows; Column: ODS silica gel column (4.6 x 150 mm) Eluent: methanol : water = 95 : 5 (containing each 0.1 % of acetic acid and triethylamine) Flow rate: 1 mℓ/min. Detecting wavelength: 254 nm Sulfur was eluted after about 6.5 minutes. The determination was conducted by the absolute calibration curve method, and the detectable limit was 1 ppm. Photosensitive difference measuring method: The decrease of photosensitivity of a blue photosensitive layer (BL) was measured using a sample kept at room temperature as the standard. The exposure value E of the fogging density value plus 1.0 was determined by the result of the density of the sample kept at room temperature. The density value in the exposure value E is referred to as D₀. Subsequently, the density value of the sample kept at 60°C for three days is referred to as D₆₀, and the density difference was calculated by the formula (D₆₀-D₀). The density difference was used as the photosensitive difference. The above results indicate that the example the sulfur content of which was small had a very small photosensitive difference and little deterioration of the photographic properties.

Claims: A cartridge for photographic photosensitive materials comprising a cartridge body, a spool and a photographic photosensitive material, wherein the internal volume of the cartridge is not more than 0.07 X cm³, wherein X is the surface area in cm² of the photosensitive layer of the photographic photosensitive material contained therein, the internal volume being the void space between the inner surface of the cartridge body and the outermost surface of the photosensitive material contained in the cartridge body, characterized in that the cartridge body is made of a plastic material having a sulfur content of not more than 2.5 µg/g. The cartridge of claim 1 the internal volume of which is not more than 0.05 X cm³. The cartridge of claim 1 wherein the plastic material of the cartridge body contains 0.05 to 15.0 wt.% of carbon black produced from petroleum material at more than 1300°C, or produced from a natural gas or vegetable oil. The cartridge of claim 3 wherein the carbon black is thermal black or channel black. The cartridge of claim 3 wherein the carbon black is produced from petroleum as the raw material at more than 1300°C for 0.02 second of the passing time through a furnace.

Inventors: MIZUNO KAZUNORI, MIZUNO, KAZUNORI, C/O FUJI PHOTO FILM CO. LTD.
Applicants: FUJI PHOTO FILM CO LTD, FUJI PHOTO FILM CO., LTD.
Application year: 1990
Main classification: G03B17
IPC codes: G03C3, G03B17, C08L101, C08K3