JPS6161096B2 - - Google Patents

Description

[Detailed description of the invention]

In the present invention, when packaging a silver halide photographic light-sensitive material containing a fluorine-based compound, the paper used to sandwich the light-sensitive material contains an inorganic salt compound, and the water content is adjusted to 2 to 10% by weight. It also relates to a method of packaging the product under conditions of a temperature of 18 to 30°C and a relative humidity of 40 to 60%. In recent years, the need to use automatic packaging machines when processing silver halide photographic materials (hereinafter referred to as "photosensitive materials") has rapidly increased due to reasons such as increasing production volume and reducing production costs. has been done. However, especially when packaging using an automatic packaging machine, there are many opportunities for the parts of the automatic packaging machine, such as metal rolls, plastic or rubber conveyor belts, to come into contact with the photosensitive material being conveyed. It is also true that packaging speeds increase and this is a cause of malfunctions. Among the various types of failures, the most typical failure is static failure, and countermeasures for this failure include replacing the rolls of automatic packaging machines, wrapping the rolls in antistatic cloth, and selecting appropriate belt materials. At present, we are forced to take various measures such as increasing the air conditioning conditions during packaging and setting the humidity as high as possible. For example, if you set the air conditioning conditions to conditions where static failures will not occur at all,
(In other words, high humidity) may cause stickiness between the photosensitive material and the paper, or between the photosensitive materials themselves.
There is a certain limit to the air conditioning conditions (under high humidity), which can cause problems such as poor transportation due to decreased transportability of the photosensitive material, and the photosensitive material becomes easily scratched. On the other hand, if antistatic processing is attempted on the photosensitive material side, it becomes necessary to add a large amount of antistatic agent in order to completely prevent static failure, which in turn may cause unnecessary fogging on the photosensitive material. The reality is that it is difficult to prevent static failures using photosensitive materials alone, as this can cause failures such as static failures and deterioration of storage stability. Furthermore, depending on the material, the amount of charge increases depending on the material of the paper used for sheet-like photosensitive materials to prevent scratches, etc., and there are also problems such as fogging on the photosensitive materials due to discharge on the photosensitive material or machines etc. There is. In recent years, it has been known that fluorine-based compounds are added to photosensitive materials to prevent static electricity, and their merits are well recognized. Furthermore, photosensitive materials containing fluorine-based compounds have great advantages when used in photosensitive materials, such as being able to reduce the amount of charge on neoprene rubber, metals, etc., and also having a significant anti-stick effect. Therefore it is widely used. However, when a photosensitive material containing this fluorine-based compound is packaged using a paper wrapper using an automatic packaging machine, the amount of charge between the photosensitive material and the sandwich paper tends to increase. That is, a phenomenon is observed in which the photosensitive material becomes negatively charged, and the amount of charge accumulates and is discharged in the photosensitive material accumulation area on an automatic packaging machine. This tendency is particularly strong in large-sized photosensitive materials such as X-ray photosensitive materials and photosensitive materials for printing, and often causes serious problems in manufacturing. As a result of studies to solve the above problem, the present inventor found that
A sheet-like photosensitive material containing a fluorine-based compound and a matting agent in the outermost layer is coated with an inorganic salt compound of 0.1
The above-mentioned problem can be solved by packaging at a temperature of 18-30°C and a relative humidity of 40-60% using paper containing ~10mg/ ^100cm2 and a moisture content of 2-10% by weight. I found a solution. Any inorganic salt compound may be used as the inorganic salt compound contained in the paper of the present invention, but preferably lithium, sodium, potassium, magnesium, calcium, lead, iron, copper, zinc, aluminum, tin, strontium, and manganese are used as the inorganic salt compound. It is an inorganic salt compound consisting of a salt of at least one selected element, and among them, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, iron chloride, and chloride are particularly preferably used from the viewpoint of effectiveness and economy. hydrochlorides such as copper; nitrates such as potassium nitrate, magnesium nitrate, lead nitrate and zinc nitrate; sulfates such as sodium sulfate, aluminum sulfate, magnesium sulfate and iron sulfate; phosphates such as potassium hydrogen phosphate and sodium phosphate; These include borates, such as potassium borate, and bromides, such as sodium bromide and lithium bromide. The above compound may contain water of crystallization. In order to use these inorganic salt compounds for paper,
Although any method may be used, a typical method is to impregnate paper by immersing it in an aqueous solution of these inorganic salt compounds during production. Regarding the amounts of these inorganic compounds used,
The amount is preferably in the range of 0.1 to 10 mg per 100 cm ² of paper. If it is less than 0.1 mg/100 cm ² , the antistatic performance is insufficient, and if it is more than 10 mg/100 cm ² , the paper and the photosensitive material may become sticky during storage. This may cause unnecessary fogging. The reason why the inorganic salt compound of the present invention reduces the charge in the film stacking section on the automatic packaging machine is probably because the use of the inorganic salt compound improves the conductivity of the sandwich paper. It can be done. By the way, 1 mg of sodium chloride/
The conductivity of the 100 cm ² paper used was 4 x 10 ¹⁰ Ω at 23°C and 55% RH as a surface resistivity value, and the charge decay time was such that a 50 V charge decreased to 2 V in 10 seconds. The moisture content referred to in the present invention is defined as follows. (Weight of the paper before drying) - (Weight of the paper after drying) / (Weight of the paper before drying) x 100 = Moisture content (%) The weight after drying is the weight of the paper after drying at a temperature of 105℃ for 3 hours. , measured at room temperature after cooling. The water content of the paper of the present invention may be 2 to 10% by weight, preferably 2% to 8%, particularly preferably 3 to 7%. If the moisture content is too low, it may cause static failure during packaging, while if it is too high, the photosensitive material may fog up due to contact over time, or the photosensitive material and the paper may stick together during high humidity such as during the summer season. or
Therefore, the present invention uses an inorganic salt compound in an amount of 0.1 to 10 mg/100 ^cm2.
By packaging a photosensitive material containing a fluorine compound and a matting agent in the outermost layer using paper with a moisture content of 2 to 10%, antistatic
This is intended to reduce fog and prevent the paper from sticking to the photosensitive material. Next, any matting agent can be used in the present invention, such as silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid, and esters thereof. , polyvinyl resin, polycarbonate, styrene polymers and copolymers thereof, etc. Generally, the particle size of the matting agent used is preferably 0.01 to 10 μ, and the amount added is generally 10 mg/100 mg/m ² used in The following fluorine-based compounds for use in the present invention are (1)
Alternatively, the compound (2) is mentioned as a preferable compound. 1 having one or more hydrophobic hydrocarbon chains having 6 to 30 carbon atoms, and at least one hydrophilic anionic group, hydrophilic cationic group, hydrophilic nonionic group, hydrophilic betaine group Or a compound containing a hydrophilic N-oxide group, wherein at least one hydrogen atom of the hydrocarbon group is substituted with a fluorine atom. 2 A polymer containing a fluorine atom, in which at least 20 mol% of the repeating units constituting the polymer is a monomer containing a fluorine atom, and 0 to 80 mol% is a hydrophobic non-fluorinated monomer, a hydrophilic monomer anionic monomer, hydrophilic cationic monomer,
A compound characterized in that it is a polymer made from a monomer selected from a hydrophilic nonionic monomer or a hydrophilic betaine monomer. Specific examples of the fluorine-based compounds of the present invention are listed below. (1) As a low molecular compound, As a compound of (2) The above-mentioned fluorine-based compound is added to the hydrophilic colloid layer in the photosensitive material, and the amount added to the hydrophilic colloid layer is generally 0.1 to 10% by weight based on the dry colloid amount of the added layer. %, preferably 0.5 to 5% by weight. The hydrophilic colloid layer that can be added may be any hydrophilic colloid layer, but preferably it is a protective layer (or outermost layer), and it can be added to other layers as long as it can diffuse into these layers. May be applied. In addition, in the layer where the fluorine-based compound is present, saponin as a coating aid, a nonionic and anionic surfactant containing polyalkylene oxide, or a surfactant such as a dialkyl sulfocorctate or a salt of arol sulfonic acid may be added. May contain. Further, it is preferable that the photosensitive material of the present invention contains a compound represented by the following general formula as a coating property improver. [In the formula, R: a hydrogen atom or a methyl group, M is a hydrogen atom or an alkali metal (lithium, potassium,
(sodium, etc.) or ammonium salt. ] This product is used as a viscosity modifier for coating liquids, and is essential for improving coating performance, but it has the disadvantage that it tends to stick to photosensitive material paper. The present invention is capable of preventing the photosensitive material from sticking to the paper even if it contains the compound represented by the above general formula. Various hydrophilic colloids including gelatin are used as binders for photosensitive materials to which the present invention is effectively applied. In this case, gelatin includes not only gelatin but also derivative gelatin, and examples of derivative gelatin include, for example, a reaction product of gelatin and an acid anhydride, a reaction product of gelatin and isocyanate, or a reaction product of gelatin and an active halogen atom. Reaction products with compounds, etc. are included. Examples of acid anhydrides used in the reaction with gelatin include maleic anhydride, phthalic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride,
Succinic anhydride, etc. are included, and isocyanate compounds include, for example, phenyl isocyanate, p
-bromophenyl isocyanate, p-chlorophenyl isocyanate, p-tolyl isocyanate, p-nitrophenyl isocyanate, naphthylisocyanate, and the like. Furthermore, examples of compounds having active halogen atoms include benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-phenoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, m-sulfobenzoyl dichloride, naphthalene-β-sulfonyl chloride,
p-chlorobenzenesulfonyl chloride, 3-
Nitro-4-aminobenzenesulfonyl chloride, 2-carboxy-4-bromobenzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2-amino-5-methylbenzenesulfonyl chloride, phthalyl chloride,
Included are p-nitrobenzoyl chloride, benzoyl chloride, ethyl chlorocarbonate, furoyl chloride, and the like. In addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, colloidal albumin, agar, gum arabic, dextran, alginic acid, such as acetyl content, may be used as a hydrophilic colloid to prepare a silver halide photographic emulsion.
Cellulose derivatives such as cellulose acetate hydrolyzed to 19-26%, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinyl cyanoacetate copolymers. , polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, etc. These hydrophilic colloids can also be used to prepare constituent layers of light-sensitive materials other than emulsion layers, such as intermediate layers, protective layers, filter layers, backing layers, etc. The light-sensitive material to which the present invention can be applied may be, for example, any type of black-and-white photographic material, color photographic material, or false color photographic material;
Examples include photographic materials that can be used for X-rays, radiation, and the like. The silver halide emulsions used in these light-sensitive materials are sensitive to all types of silver halides, including silver chloride, silver iodide, silver bromide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. salts of noble metals such as ruthenium, rhodium, palladium, iridium, platinum, gold, etc., such as ammonium chloroparadate, potassium chloroplatinate, potassium chloroparadite, potassium chloroaurate. Various chemical sensitizations can be carried out, such as noble metal sensitization using sulfur compounds, reduction sensitization using stannous salts, polyamines, etc., and sensitization using polyalkylene oxide compounds. This emulsion can also be optically sensitized with cyanine dyes, merocyanine dyes, complex cyanine dyes, etc., and can also be optically sensitized with various couplers such as colorless couplers, colored couplers, development inhibitor releasing couplers, etc., as well as mercury compounds, triazoles, etc. stabilizers such as azaindene-based compounds, benzthiazolium-based compounds, zinc compounds, hardeners such as mucohalogenic acids, vinyl sulfone compounds, and co-existence of alkylacrylates or alkyl methacrylates with acrylic acid or methacrylic acid. Film property improvers comprising water-dispersible fine particulate polymeric substances obtained by emulsion polymerization of polymers, styrene-maleic acid copolymers, styrene-maleic anhydride half-alkyl ester copolymers, etc., such as saponin, Coating aids such as polyethylene glycol lauryl ether, wetting agents such as compounds such as those described in U.S. Pat. diglycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 2.4.
7,9-tetramethyl-5-dency-4,7-diol, 3,6-dimethyl-4-octyne-3.
6-diol, propylene glycol, hexylene glycol, pentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol,
Various other photographic additives such as 1,2-cyclohexanedimethanol, 1-methyl-3,4-cyclohexanediol, 4-hydroxycyclohexanemethanol, trimethylolethane, trimethylolpropane, etc. can also be added. As mentioned above, the method of the present invention can be applied to any photosensitive material. For example, when packaging sheet-like photosensitive materials, the photosensitive materials are laminated and the paper of the present invention is sandwiched between the photosensitive materials. packaged. When packaging a roll-shaped photosensitive material, the roll-shaped sandwich paper of the present invention is rolled up and packaged together with the roll-shaped photosensitive material, for example, in a hatron. The present invention will now be illustrated by the following examples, but the embodiments of the present invention are not limited thereto. Example Silver iodobromide containing 2.0 mol% of silver iodide was used to gold sensitize a gelatin high-sensitivity emulsion during the second ripening, followed by an azaindene compound as a stabilizer, formalin as a hardening agent, and saponin as a coating aid. and Compound (A) were added to prepare a coating solution. Compound (A) Next, formalin was used as a hardening agent, and a polymethyl methacrylate pearl copolymer with an average particle size of 3 μm and colloidal silica were used as matting agents.
AM (trade name: manufactured by Dupont) as a coating aid
Prepare an aqueous gelatin solution containing C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₉ H at 0.03 g/unit Gel, divide it into 4 parts,
Exemplary compounds 1-(3), 1-(28) and 2-(27) of the present invention were added to each of the three materials at 0.025 g/unit gel to prepare a coating solution for the protective film, and the coating solution for the emulsion layer was added to the lower layer. A film sample was prepared by simultaneously coating polyethylene terephthalate in multiple layers, applying it to both sides, and drying it. On the other hand, the paper was impregnated with a 0.5% aqueous sodium chloride solution so that the amount of sodium chloride was 1 mg/100 cm ² . We also prepared blanks that were not processed. A packaging test was conducted using an automatic packaging machine using the samples and paper clips prepared as described above. The conditions are as follows. Packaging conditions (1) 20℃ 65%RH (2) 20℃ 50%RH (3) 20℃ 30%RH (RH: relative humidity) Static failures in Table 1 were determined using the following method. (1) In the film stacking section of the automatic packaging machine, measure the amount of charge when 50 samples are stacked between paper clips. Measurement is carried out using the product name Statylon current collector potential measuring device.
The test was carried out using a KS-325 model (manufactured by Kasuga Denki KK). (2) Peel only the sample from the collected sample and the sandwich paper using the same method every time, check whether or not there is a sound of discharge sparks, and then develop it.
Check for static marks. (3) For reference, measure the amount of frictional charge between the sample and neophrene rubber. Films accumulated due to non-static failures were sealed using a barrier bag and heat treated at a temperature of 45°C for 12 hours to judge photographic performance and serve as a surrogate for a shelf life test. In addition, in order to determine the degree of stickiness between the paper and the sample due to the increase in the moisture content of the paper, we layered 50 samples sandwiched on paper, sealed them with a barrier bag, and After heat treatment at 55°C for 84 hours, the degree of stickiness or stickiness between the paper and the sample was determined. This was done on the assumption that there is a risk of the paper and sample sticking together during storage when the packaging humidity is high (high temperature and high humidity in summer). The above results are listed in Table 1. As can be seen from the table, by combining the sample of the present invention, the sandwich paper, and the air conditioning conditions of the packaging, it is possible to provide the best combination in terms of the degree of static mark generation, stickiness, and photographic performance.

[Table] Example A silver iodobromide gelatin high-sensitivity emulsion containing 2.0 mol% of silver iodide was gold sensitized during the second ripening, using an azaindene compound as a stabilizer, glyoxal as a hardening agent, and saponin as a coating aid. was added to prepare a silver halide emulsion. Divide this emulsion into two
(A) and (B). (A) is used as a coating solution as it is, and (B) is further added with the compound (A) shown in the general formula of the present invention as a coating aid.
0.8 g/unit of Gel was added to prepare a coating solution. Next, formalin was added as a hardening agent, and polyoxyethylene lauryl ether was added as a coating aid at 0.04 g/unit.
Gel, an aqueous gelatin solution containing 50 mg/m ² of polymethyl methacrylate with an average particle size of 4.5 μm as a matting agent and colloidal silica (trade name Ludotux AM manufactured by DuPont) with an average particle size of 14 μm as a 0.8 g/m ² film. Adjust, divide this into four, (1),
(2), (3), and (4). Among these, (1) and (3) are exemplary compounds of the present invention as antistatic agents.
Add 0.02g/unit Gel to each of (29), add no antistatic agent to (2) and (4), prepare as a coating solution for the protective film, use the coating solution for the emulsion layer as the lower layer, and apply the emulsion layer. Coating liquid (A) with protective layer coating liquids (1) and (2) and emulsion layer coating liquid (B) with protective layer coating liquids (3) and (4) were applied simultaneously on polyethylene terephthalate. This was applied to both sides and dried to prepare a sample.
On the other hand, impregnate a piece of paper with a 0.6% CaCl ₂ aqueous solution.
It was processed so that CaCl ₂ was present at 1.5 mg/100 cm ² .
In addition, as a blank, one in which CaCl ₂ was not processed was also prepared. A packaging test was carried out using an automatic packaging machine using the samples and paper clips prepared as described above, and the degree of static failure was observed. At the same time, other failures were also observed. The results are shown in Table 2.

【table】

Claims (1)

[Scope of Claims] 1. A silver halide photographic material containing a fluorine-based compound and a compound represented by the following general formula, and a matting agent in the outermost layer, is treated with an inorganic salt compound.
Using paper containing 0.1 to 10 mg/100 ^cm2 and a moisture content of 2 to 10% by weight, at a temperature of 18 to 30°C and relative humidity.
A method for packaging silver halide photographic materials, characterized by packaging them under conditions of 40 to 60%. general formula [In the formula, R represents a hydrogen atom or a methyl group,
M represents a hydrogen atom, an alkali metal or an ammonium salt. ]