JP2899816B2 - Roll film for photography - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a technical means for improving light-shielding paper of a photographic roll film and preventing loose winding.

[Conventional technology]

As shown in the development of FIG. 1, a photographic roll film of 120 type, 220 type, 620 type, etc. is obtained by winding the light-shielding paper 3 and the silver halide photosensitive film 12 together on the spool 1 and wrapping the sealing paper 4a at the end. Is stuck to prevent unraveling. Therefore, the silver halide photosensitive material film 12
Is protected from light by a spool flange and light-shielding paper.

However, if there is a slight gap between the spool flange and the light-shielding paper, light leaks and a failure occurs. This shielding width dimensions as the flanges inner dimension between l ₁ of the spool 1 or 10 exactly the same when wound on take-up spool 10 of the same dimensions as the spool 1 loaded in the camera, as shown in FIG. 2 l ₂ does not meet the original function of the light-shielding is not necessarily more of the same or a light shielding sheet width dimension l ₂ is wider than the.

However, if the light-shielding paper width dimension l ₂ that satisfies this condition is much larger than the inner dimension l ₁ between the spool flanges, the light-shielding paper will have a large resistance to fit between the flanges, resulting in a loose winding and severely If this happens, the camera may be stopped in the camera due to the occurrence of curling or the light-shielding paper rising on the outer periphery of the flange.

How to severely increased or flange inside between the management of dimensions l ₁ and the light-shielding width dimension l ₂ flexibility backing paper have been taken to improve this like.

[Problems to be solved by the invention]

As a measure to prevent loose winding, if the thickness of the base paper is reduced to increase the flexibility of the light-shielding paper, the number of pinholes increases and the light-shielding property is reduced or the strength is reduced. If the flexibility is increased too much, there is a drawback that when the tip of the light-shielding paper is inserted into the slit of the spool, it is difficult to insert the light-shielding paper and the operability is deteriorated.

In order to compensate for such a drawback for reducing the thickness of the base paper, a method of processing the back surface with a resin may be considered. One method is to laminate a resin film. This significantly increases the cost and, as described in Japanese Utility Model Application No. 62-186708, hinders the application of heat sealing at the end of the roll film winding and packaging process to prevent the light-shielding paper from breaking. It becomes.

However, although it is recognized that this method does not impair light-shielding properties and has a tendency to have some degree of flexibility, it is still technically insufficient by itself, and strict control is still required for the light-shielding paper width dimension and the spool flange inner dimension. It is at the level.

In addition, the dimension l ₁ between the inner sides of the two flanges of the spool is less than a good product unless it is managed with a certain width in consideration of expansion and contraction of the resin at the time of molding. .

Then, for raising the dimensional accuracy of the light-shielding sheet width dimension l _2, since the dimensions of the backing paper is highly dependent on temperature and humidity, producing at constant temperature and humidity, processing, storage, and be packaged in the year conditions Becomes very difficult. Further, regarding black paper containing carbon, it has been considered that it is actually impossible to control the paper width dimension because the on-line moisture content measurement is difficult with current technical equipment.

In addition, 120-type and 220-type photographic roll film cameras have been used by professionals in the past, and there were few problems due to the familiarity with the camera. It is becoming popular in the meantime. At the same time, for example, the operation of firmly winding the film around the spool while holding the light-shielding paper by hand until the start mark is set after the film is loaded is not always executed.

Due to such a situation, troubles in the camera of the photographic roll film having the light-shielding paper are constantly occurring.

The light-shielding paper used for the roll film is usually printed or processed with resin using paper as a base material. Paper is generally susceptible to moisture, and its dimensions change with its moisture content. The effect of this change on the light-shielding paper for a roll film is very large, and the influence greatly affects the quality of the roll film. In addition,
The paper expands and contracts much more in the width direction (width) than in the papermaking direction (vertical), so that the light-shielding paper comes closer to the width dimension, so that the fluctuation is considerably large. In order to minimize these effects, the following may be considered.

Double-sided resin processing (10 μm or more) Single-sided resin processing (15 μm or more) Reduce the paper layer thickness and increase the resin layer thickness to reduce the proportion of paper from the entire light-shielding paper.

However, this has the following disadvantages.

Cost increase Although temporary expansion and contraction is prevented, the magnitude of the fluctuation is the same as in the past, and it cannot be prevented for a long time.

The strength, flexibility, and handling characteristics unique to paper are lost, and the function of the light-shielding paper is reduced.

In the present invention, the relationship between the moisture content of the light-shielding paper and the fluctuation of the width of the light-shielding paper during processing, that is, the relationship between the light leakage and the light leakage due thereto, is tested under various atmosphere substitute conditions. If the inexperienced user uses a roll film of 120, 220 type, etc. for the camera in general, no trouble such as light leakage, loosening, and wrapping will occur, and stable transport in the camera will be performed. It is an object of the present invention to provide a photographic roll film showing the following.

[Means for solving the problem]

The purpose of this is to use silver halide photosensitive material film, light-shielding paper,
And in a photographic roll film comprising a spool having a flange, the width dimension of the light-shielding paper wound around the spool together with the photosensitive material film is the same as or larger than the dimension between the flange inner sides, and This is achieved by a photographic roll film, wherein the water content of the light-shielding paper is 5.0 to 6.0 wt%.

〔Example〕

 Hereinafter, the present invention will be described more specifically.

The base paper used for the light-shielding paper used in the present invention may be any of ordinary natural pulp paper, synthetic resin or synthetic paper using a synthetic resin, but may be wood such as softwood pulp, hardwood pulp, and softwood hardwood mixed pulp. Natural pulp paper based on pulp is advantageously used. These papers may be formed by any of the generally known round net forming method and fourdrinier forming method. These base papers containing natural pulp as a main component can contain various polymer compound additives. For example, as a dry paper strength agent, cationized starch,
Cationic polyacrylamide, anionic polyacrylamide, carboxy-modified polyvinyl alcohol, gelatin, etc., as sizing agents, fatty acid salts, rosin derivatives,
Dialkylketin dimer emulsions, petroleum resin emulsions, ammonium salts of styrene-maleic anhydride copolymer alkyl esters, etc., as pigments, clay, kaolin, calcium carbonate, barium sulfate, titanium oxide, etc.
As a wet paper strength enhancer, melamine resin, urea resin, epoxidized polyamide resin, as a fixing agent, a polyvalent metal salt such as aluminum sulfate and aluminum chloride, a cation-modified polymer such as a cation-valent starch, etc., as a pH regulator, as a caustic soda , Sodium carbonate, hydrochloric acid, etc., as inorganic electrolytes,
Salts, sodium sulfate, and the like, as well as dyes, fluorescent brighteners, latex, carbon black, and the like can be appropriately combined and contained.

Even if a resin layer is laminated in order to impart physical properties that cannot be obtained with paper alone, it may be acceptable.

As the thermoplastic resin for processing the back side of the base paper (hereinafter sometimes simply referred to as resin), Japanese Patent Publication No. 51-49205, Japanese Patent Application Laid-Open Nos. 48-22020, 50-676644, and 55-140835 , Id 58
-17434, 58-186744, 59-68238, 60-35728
No., low-density, medium-density, high-density, linear low-density various polyolefins such as polyethylene and polypropylene, polyvinyls such as ethylene vinyl acetate, acrylics such as ethylene ethyl acrylate and ethylene methyl acrylate, styrene- A simple substance such as a rubber type such as butadiene, a simple substance such as ionomer, a graft polymer polyamide type, or a polyester type such as polyethylene-terephthalate.
Blends or copolymers of more than one kind may be mentioned. The above resin may be provided as two or more layers.

When these resins are laminated on the base paper, an anchoring agent may be used to further enhance the adhesiveness. Examples of the anchoring agent include organic titanium-based, isocyanate-based, polyethyleneimine-based, and polybutadiene-based agents.

Means for providing these resins on a paper support can be broadly classified into two methods.

One of the methods is a method in which a liquid in which a resin is dispersed or dissolved in an organic solvent, water, or the like is applied to paper and dried.

For example, the coating method can be applied by a reverse roll method, a blade method, an air knife method, a rod method, a curtain method, an extrusion method, gravure printing, or the like, but is not limited thereto.

The dry thickness of the resin layer obtained by these methods is suitably from 1 to 20 μm.

As another method, there is a method in which a resin is melted by heat and provided on a paper support. The most common application method is the extrusion method, but other application methods may be used.

 There is also a dry laminate type.

The dry thickness of the resin layer obtained by this method is 5 to
50 μm is appropriate.

The most advantageous method in the present invention is the former method of applying a dispersion or solution. In this method, there is no need to consider the softening point of the applied resin so much that the softening point is not limited and a wide range can be selected. Also, a resin having a high softening point can be applied. However, in the case of the latter hot-melt coating, a resin having a limited resin softening point and having a relatively high softening point must raise the melting temperature, and a special coating process is required. In consideration of the adhesiveness between paper and resin, the former method is generally superior to the latter method.

In addition, the effects disclosed in Japanese Utility Model Application No. 62-186708 can be easily combined, resulting in a more comprehensive improvement.

Carbon black used in the resin layer, paper layer, or other layers in the present invention includes a furnace, a channel,
It may be manufactured by any method of thermal.

Examples of actual products include, for example, carbon blacks # 5, # 20, # 33, # 40, # 44, # 52, #
900, # 1000, # 2200B, # 2350 #, # 2400B, MA8, MA10
0 and the like are not limited thereto.

Characters and symbols necessary for the function are printed on the surface of the light-shielding paper, or printing is performed to enhance the commercial value, but the ink used for these printing is selected as harmless to the photosensitive material and is generally used It can be selected from among offset printing ink, gravure printing ink or UV ink.

Typical synthetic resins used for these inks are polyvinyl chloride, nitrified cotton, polyester, polyamide urethane,
Polyacrylic, rosin modified maleic acid, ethylene vinegar,
Vinyl ether, urethane vinegar, salt vinegar biurethane resin, modified alkyd resin, modified phenolic resin, alkali-soluble resin (rosin-modified maleic resin, styrene maleic resin, styrene acrylic resin, acrylate acrylic resin, methacrylic acid Ester acrylate resin), hydrosol type resin (styrene maleate resin, styrene acrylate resin, α-methyl styrene acrylate resin, acrylate acrylate resin, methacrylate acrylate resin), emulsion type resin (styrene resin, Styrene acrylate resin,
Acrylic ester copolymer resin, methacrylic ester copolymer resin), and polymers with acrylic unsaturated groups are commonly used as resins for UV inks. Typical examples are polyester / acrylate esters. , Polyester / urethane resin / acrylate, epoxy resin / acrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, and hydroxyethyl methacrylate. Can be

A commonly known coloring agent is used in combination with these inks. As the colorant used, Japanese Patent Application No. 61-18942
No. 5 various pigments and azo pigments (azo lake; carmine 6B, red 2B, insoluble azo; monoazo yellow (PY-1, -3), disazo yellow (PY-12, -13, -14,-
17, -83), pyrazolo orange (PO-B-34), vulcan orange (PO-16), condensed azo type; chromophtalerylo (PY-93, -95) chromophthal red (PR-144, -166) ,
Polycyclic pigments (phthalocyanine-based; copper phthalocyanine blue (PB-15, 15-1, -15-3), copper phthalocyanine green (PG-7), cyoxazine-based; dioxazine violet (PV-23), isoindolinone System: isoindolinone yellow (PY-109, -110), sulene system: perylene, perinone, flavantron, thioindigo, lake pigment (malachite green, rhodamine B, rhodamine G, Victoria blue B) or inorganic pigment (oxide, Precipitable barium sulfate, carbonate; precipitated calcium carbonate, silicate; hydrated silicate, anhydrous silicate, metal powder; aluminum powder, bronze powder, zinc powder, carbon black, Examples of such materials include yellow lead, navy blue, etc. These compounds may be added as a light-shielding substance to the above-mentioned resin layer, paper layer, etc. In addition, oil-soluble dyes, Other materials such as solvents, dispersants, wetting agents, defoamers, leveling agents, thickeners, stabilizers, cross-linking agents, waxes, dryers, etc. are also used as raw materials for the ink. Additives are used.

Also, a varnish may be applied to protect the surface gloss and the printed portion on the surface. The type of varnish used at this time is an acrylic resin layer, a cellulose resin such as cellulose acetate,
Urethane resin, epoxy resin, polyester resin, ionomer resin, EEA resin, various polyethylene resins (low density,
Suitable resins such as high-density, linear low-density polyethylene, and polypropylene resins can be used. Also, wax and the like can be used.

The present applicant has made the first among the light-shielding papers thus configured.
As shown in the table, select 13 types by combining the forming method of the back surface processing, the material used and the film thickness, and for each of them, use the specific method and solvent for the paper on the specific side and further use the specific plate A light-shielding paper for a 120-type roll film was prepared so as to have a specific finished water content by making it deeper.

Using this light-shielding paper, 30 negative color films made by Konica and having a sensitivity of 3200 were installed, each with a relative humidity of RH.
However, after being left for about 1 hour under the air conditioning conditions of 20%, 55% and 80%, a real photography test was performed with a camera. After that, a 10,000-lux bomb was given to develop, and light leakage was checked.

The pass / fail judgment conditions are as follows. First, if there is at least one light leaking to the screen, it is determined to be x, and if the film is wound up during shooting and cannot be wound up, it is determined to be x. If more than 3 out of 30 are recognized,
も の indicates that no light leakage was observed.

Then, the anti-emulsion property was taken as the second pass / fail judgment condition. That is, the 120-type roll film prepared above was subjected to thermoprocessing and then developed, and the fog density was measured for each of the B, G, and R layers. Test No. 6 was used as a sample of the conventional standard treatment. Compared to this, Δ was determined when at least one layer was +0.05 or more, X was determined when +0.1 or more, and O was determined when +0.04 or less.

 The results are shown in Table 2.

It can be said that if the finished water content is in the range of 5.0 to 6.0 wt%, more preferably 5.2 to 5.8 wt%, the actual test is good and the fog density is in the acceptable range.

When the water content is 5.0 wt% or less, the elongation after the cutting step of slitting the light-shielding paper from a wide width to a width of one product becomes large. Accordingly, the width of the light-shielding paper before dispersion increases, and in addition, the light-shielding paper absorbs moisture during storage or photographing at a high temperature after the product, and the width of the light-shielding paper increases. Therefore, there is a possibility that the suitability of the camera may be degraded due to problems such as occurrence of winding and a high hoisting torque.

When the water content is 6.0 wt% or more, the width dimension is stable, but there is a high possibility that moisture will be released from the light-shielding paper during storage or photographing at low temperatures before interior decoration or after the product has been shrunk. This results in light leakage. Also, in terms of emulsion resistance, the film deteriorates with time and the fog density rises abruptly as compared with the case where the water content is 6.0 wt% or less.

Next, means for achieving a water content of 5 to 6% by weight will be described. Shading paper is usually made after paper making, calendaring and printing,
Resin processing is performed, and heat is applied for each processing. Therefore, the water content of the paper tends to decrease gradually, especially when the backside resin processing is performed,
It may be 4wt% or less. Above all, a case where lamination is performed can be said to be a typical example of these.

However, in recent years, the quality required for films has been extremely increased, and paper alone cannot cope with this as a light-shielding paper, and a method for improving the quality by adding resin processing has become indispensable. Therefore, reduction of the water content by this resin processing is inevitable.

Therefore, as a countermeasure, humidification using steam was performed. That is, in most cases, the light-shielding paper is rewound for inspection after printing, and the rewound is used to apply steam to the paper surface during the rewound to absorb moisture. The steam is most preferably ultrasonic steam using pure water, and is suitable because of its compatibility with emulsion, equipment and cost. Another typical example is steam steam, which is likely to adhere to the surface of the light-shielding paper as water droplets. It is not suitable, and it is unfavorable including cost because it is large and special as equipment.

As another method, there is a method of humidifying by applying water. As a specific means, a roll coater is used. Alternatively, use of a gravure or solid printing plate may be used. The degree of humidification varies considerably depending on the surface to be applied. In addition, there is a problem that if water alone is used, it is almost always repelled and does not enter or adheres like water drops. In order to prevent this, by mixing with an organic solvent or the like to reduce the surface tension, cissing is eliminated and the hydrophilic surface can naturally be humidified also to the hydrophobic surface. However, if a large amount of the organic solvent used at this time remains on the light-shielding paper, there is a concern that a trouble such as sticking to the emulsion surface or the like may occur after the organic solvent is wound up and built together with the film. Therefore, after this humidification, it is necessary to dry and remove the organic solvent. At this time, if an excessively high temperature is applied, the water that has been humidified will be expelled and the humidification effect will be reduced by half. Water azeotropes with organic solvents,
Since there is a problem that the solvent evaporates to some extent even at a low temperature, it is preferable to select an organic solvent having a low boiling point as much as possible. The organic solvent is not particularly limited as long as it is well mixed with water and has a low boiling point, but methanol is most preferable and easy to handle in consideration of cost and the like. In addition, the mixing ratio with water is preferably about 3: 7 to 7: 3. When water exceeds 7, the effect of adding an organic solvent is lost, and when water is less than 3, azeotropic problems and residual solvents increase. And other problems arise. The type and mixing ratio of these organic solvents are set according to the state of the material on the surface to be humidified.

In the case of laminated light-shielding paper, the laminated surface hardly absorbs moisture and has little effect, so it is preferable to perform it on the printed surface of the front, and if printing after lamination, use the last unit of multicolor printing This humidification can be performed online.

At this time, it is necessary to confirm that the ink used for table printing does not dissolve in the used organic solvent.

The same applies to the case of light-shielding paper that has been resin-processed by coating.However, when the backside resin processing is performed with a printing machine, the resin layer thickness is thinner than the laminate, and is generally more porous than the layer formed by the laminate. Because of the quality, humidification is possible on both sides. Therefore, it can be performed in the final unit at the time of front surface printing after front printing, can be processed online, and can be said to be the preferred mode in the best order in consideration of loss and the like.

Although steam humidification is advantageous in terms of cost, the humidification level is low and is inferior to humidification with water. The latter also
In most cases, the moisture is absorbed once, but dried instead of drying. At this time, the paper absorbs and desorbs moisture, and the hysteresis of the paper material causes the level of expansion and contraction to be lower than before moisture absorption and desorption, which is very advantageous for light-shielding paper. In other words, after drying with water, 6.0w
Water content is reduced from t% to 5.5% by weight, while water is increased only by moisture absorption to 5.3% by using steam. Can be expected. Therefore, regarding the humidification method, a method of applying water can be said to be the most effective means for achieving the present invention. However, it is also possible to selectively use both at the level of the moisture content of the light-shielding paper before humidification as described below. For example, if the moisture content of the shading paper finish (without humidification) is 4.5 to 4.9 wt%, use steam humidification and 4.
If it is 5 wt% or less, it is preferable to use printing humidification, and considering seasonal fluctuations, it is preferable to use steam humidification at the time of high humidity in summer and print humidification at the time of drying in winter.

〔The invention's effect〕

According to the present invention, it is possible to stabilize the variation in the width of the light-shielding paper wound between the flanges of the spool so that light leakage does not occur, and troubles such as loose winding, loose winding, and lifting of the flange which have often occurred in the past. The phenomenon has completely disappeared, and the fogging phenomenon and the poor transportation phenomenon in the camera can be avoided.

[Brief description of the drawings]

FIG. 1 is a developed plan view of a 120 type photographic roll film. FIG. 2 is a view showing a 120 type photographic roll film when a camera is loaded. 1,10 Spool 3 Shielding paper 4a Sealing paper 12 Photosensitive film of silver halide material l ₁ ...... Width between spool flange inner sides l ₂ ...... Shielding paper width

Claims (1)

(57) [Claims] 1. A silver halide photosensitive material film, a light-shielding paper,
And in a photographic roll film comprising a spool having a flange, the width dimension of the light-shielding paper wound around the spool together with the photosensitive material film is the same as or larger than the dimension between the flange inner sides, and A roll film for photography, wherein the water content of the light-shielding paper is 5.0 to 6.0 wt%.