JP3282041B2 - Packaging materials for photographic photosensitive materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wrapping material for photographic light-sensitive materials, and more particularly to a wrapping material for photographic light-sensitive materials capable of preventing performance deterioration of the photographic light-sensitive material during storage.

[0002]

BACKGROUND OF THE INVENTION Generally, a package of a silver halide photographic light-sensitive material is light-shielding, and the photographic light-sensitive material generally deteriorates due to humidity.

[0003] Usually, in order to provide a light-shielding effect, a resin in which carbon black is dispersed as a light-shielding agent is applied or laminated to a paper colored in black or a colored paper or a white paper having an incomplete light-shielding effect so as to have a required light-shielding effect. ing. In addition, letters and symbols necessary for the function are printed as needed to enhance the commercial value. The roll-shaped photosensitive material using the light-shielding packaging material whose surface has been subjected to printing processing is stored in various states until it is photographed after production. In this case, no problem occurs when stored at a low temperature of about -10 to 10 ° C, but when stored at a higher temperature for more than 6 months, fogging occurs and the performance of the photosensitive material is reduced.

[0004] Such fogging is characterized in that the fogging is concentrated on a portion of the light-shielding paper on which the design printing is performed. If such a fogged portion enters the screen, it will be a fatal defect, and if a film is printed, the color reproduction on the screen will be abnormal, and the color will be partially changed and the commercial value of the print will be significantly impaired. .
In particular, if fogging occurs on film that cannot be easily retaken, such as portraits and weddings, using 120- or 220-size film, this is a major problem. It is currently using.

As a means for suppressing the occurrence of fogging, varnish to be applied to the upper layer of the packaging material paper is prevented by applying the varnish three to five times. However, when the varnish coating is increased, there are problems that the production cost increases and that the resin film processed into the light-shielding packaging material becomes brittle or hard. When processed with such a resin,
As a result, the light-shielding packaging material becomes less flexible. Also,
When a roll film using such a light-shielding packaging material is used for a camera, there is a disadvantage that the winding torque of the camera is heavy and operability is deteriorated. In the case of the camera of the automatic winding type, the battery consumption is increased.

As a result of intensive studies, the present inventors have found that the causes of such fogging are caused by the surface condition and size of the light-shielding paper base paper and the ink used for design printing on the light-shielding packaging material surface. I found it.

[0007]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, an object of the present invention is to provide a light-shielding packaging material for a photographic light-sensitive material, which does not deteriorate the performance of the photographic light-sensitive material during storage over time. Is to provide.

[0008]

The above object of the present invention DETAILED DESCRIPTION OF THE INVENTION In the packaging material for photographic photosensitive materials, the surface of the packaging material for photographic photosensitive materials is flat <br/> Namerado 65 ～130Sec, size of 7 to 20 se c It is achieved by the packaging material for photographic photosensitive materials, which comprises using paper. Further, the surface of the packaging material is desirably processed with an ink having a weight ratio of resin to pigment of 1: 0.5 to 1: 5.

Hereinafter, the present invention will be described in detail.

[0010] As the roll-shaped photosensitive material using the light-shielding packaging material, a cartridge type roll-shaped so-called 110 size or 126 size, in which a film and a light shielding packaging material are simultaneously wound and stored in a cartridge, is used. Photosensitive material. A film is wound together on a spool almost at the center of the entire length of the light-shielding packaging material, a so-called 12
0 size film. There is a leader light-shielding packaging material at the leading end of the film and a so-called 220-size film in which a trailer light-shielding packaging material is attached to the end of the film with an adhesive paper or the like. Applied to roll-shaped photosensitive materials.

In the present invention, the smoothness refers to the flatness of the paper surface, and the measurement was performed by a method using a Beck tester according to JIS P 8119.

In the present invention, the term "size" refers to improving the surface properties of paper so as to prevent ink from bleeding and to prevent fluff, and the degree of size indicates the degree of the improvement. It was measured by the test method.

The base paper of the light-shielding packaging material used in the present invention may be any of ordinary natural pulp paper, synthetic fiber, or synthetic paper using a synthetic resin film, but may be softwood pulp, hardwood pulp, or softwood hardwood. Natural pulp paper mainly containing wood pulp such as mixed pulp is advantageously used. Papermaking of these papers may be performed by any of the generally known round net forming method and fourdrinier forming method.

Among these natural pulps, there are mechanical pulps and chemical pulps. From the viewpoint of stability in photographic performance, it is preferable to use chemical pulps. Even when mechanical pulp is used as required, the use ratio is preferably suppressed to 30% or less as much as possible.

The base paper containing natural pulp as a main component can contain various polymer compounds. For example, as a dry paper strength enhancer, cationized starch, cationized polyacrylamide, anionized polyacrylamide, carboxy-modified polyvinyl alcohol (Kuraray Co., Ltd., KM-118, KL-118, KL-318, KL-506) , Sizing agents such as gelatin, fatty acid salts, rosin derivatives, dialkylketin dimer emulsions, petroleum resin emulsions,
As pigments such as ammonium salts of styrene-maleic anhydride copolymer alkyl esters, clay, kaolin,
Calcium carbonate, barium sulfate, titanium oxide, etc., as a wet paper strength enhancer, melamine resin, urea resin, ethoxylated polyamide resin, as a fixing agent, aluminum sulfate,
Polyvalent metal salts such as aluminum chloride, cation-modified polymers such as cationized starch, etc., pH adjusters such as caustic soda, sodium carbonate, and hydrochloric acid; inorganic electrolytes such as sodium chloride and sodium sulfate; dyes, fluorescent brighteners, Latex carbon or the like can be appropriately combined and contained.

When printing is performed using these base papers,
We found that the effect on photographic performance differs depending on the condition of the base paper used. It is not clear why these phenomena occur, but the following can be considered if we dare to make inferences. If you use paper with a size of less than 7 seconds,
The resin component of the ink penetrates the paper, distributed it to remain such a state to have the pigment surface, the less amount of resin covering the pigment surface to be, as described in JP 63-44653 oxide If pigments such as titanium adversely affect the photographic performance, adversely since the covering amount of the resin is small to generate a strongly appear fog. If the size degree is 7 to 20 se c, penetration of the resin into the base paper is reduced, because the coating amount of the resin as a result the pigment surface is increased, contained in the pigment, adversely affecting the light-sensitive material The substance is considered to be stable because it is trapped in the resin and does not go outside.

[0017] Furthermore, when the smoothness of the base paper and printing surface is carried out if the print processing is less than 65Sec, sump resin into the recess, because the protrusion amount deposited resin is reduced, resulting in a pigment to be covered < The result is the same as when the size is less than 7 seconds. For smoothness of 65 to 130 DEG se c, since the offset of the resin is not uniform, so the coating of the pigment is constant,
Substances that are contained in the pigment and have an adverse effect on the light-sensitive material are trapped in the form, and are stable because they do not go outside.
However, the size of even a smoothness of 65 ~130 se c is 7sec
If it is less than this, the effect will be lost, and the effect will be obtained only by combining the smoothness and the size.

The preferred sizing degree is 7 sec to 20 sec, more preferably 8 sec to 18 sec.

The preferable smoothness is 65 sec to 130 sec.
And more preferably 70 to 110 seconds.

However, this alone is not sufficient, and the ratio of the ink to be used and the resin and pigment constituting the ink becomes important. That is, it is the ratio of the amount of resin that can be coated on the pigment surface with a sufficient thickness and the amount of the pigment to obtain a sufficient print density. According to experimentally determined results, the important ratio of resin to pigment is 1: 0.5 to It was found that 1: 5 is preferable, and a more preferable range is 1: 1 to 1: 4. In addition, if such a ratio is low, it is worn, but since the required color does not appear in the finished quality, it is necessary to mix a certain amount or more.

Printing is performed on the surface of the light-shielding packaging material in order to increase the value of characters and symbols required for the function or the commercial value. Offset printing, which is generally used as an ink for these printings, is used. Ink, or gravure printing ink, or UV ink can be used.

Typical types of synthetic resins used in these inks include nitrated cotton, polyester, polyamide urethane, polyacryl, rosin-modified maleic acid, ethylene vinyl acetate, vinyl ether, urethane vinyl acetate, and modified alkyd resin. , Modified phenolic resin, alkali-soluble resin (rosin-modified maleic resin, styrene maleic resin, styrene acrylate resin, acrylate acrylate resin, methacrylate 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 acid ester copolymer resin, methacrylic acid ester copolymer resin) and the like. Resins having a chlorine atom as a base are not preferred.

As the resin for the UV ink, a polymer having an acrylic unsaturated group is generally used, and typical examples thereof include polyester / acrylate,
Polyester / urethane resin / acrylate, epoxy resin / acrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, and hydroquinethyl methacrylate Can be

A commonly known coloring agent is used in combination with these inks. As the coloring agent used,
Various pigments described in JP-A-63-44653 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), and vulcan orange (PO-1).
6), condensed azo type; Chromophthal Yellow (PY-93, -9
5) Chromophthal Red (PR-144, -166) polycyclic pigment (phthalocyanine-based; copper phthalocyanine blue (PB-1
5, -15-1, -15-3), copper phthalocyanine green (P
G-7), dioxazine type; dioxazine violet (PV-23), isoindolinone type; isoindolinone yellow (PY-109, -110), sulene type: perylene verinone, flavantron, thioindigo, lake pigment ( Malachite green, Rhodamine B, Rhodamine G, Victoria Bull-B, and inorganic pigments (oxides: titanium dioxide, red iron oxide, sulfate; precipitated barium sulfate, carbonate,
Precipitable calcium carbonate, silicate, hydrated silicate, anhydrous silicate, metal powder; aluminum powder, bronze powder, zinc dust carbon black, graphite, navy blue and the like. In addition, oil-soluble dyes, dispersible dyes, and the like are also used. In addition, additives such as various solvents, dispersants, wetting agents, defoaming agents, leveling agents, thickeners, stabilizers, cross-linking agents, waxes, dryers and the like are used as necessary as raw materials constituting the ink.

In addition, a varnish may be applied to protect the surface gloss and the printed portion of the surface. The type of varnish used at this time includes acrylic resin, cellulose resin such as cellulose acetate, urethane resin, epoxy resin, polyester resin, ionomer resin, EEA resin, various polyethylene resins (low density, high density, linear low density , Polyethylene, etc.) Suitable resins such as polypropylene resin can be used. Also, wax and the like can be used.

The film used in the present invention is also important in terms of antistatic and camera operability. That is, the thickness of the film base is preferably 100 μm or less, and the film is easy to slip from the viewpoint of the operability of the camera, and the sliding property in contact with the light-shielding packaging material is also important. To impart these sliding properties, JP-A-62-286041,
The lubricant described in JP-A-62-286042 may be used, and the back surface is similarly configured.

As the resin for processing the back side of the base paper, Japanese Patent Publication No. 51-49205, JP-A-48-22020, JP-A-50-67644,
JP-A-55-140835, JP-A-58-17434, JP-A-58-1867
No. 44, JP-A-59-68238, JP-A-60-35728 described resins and low-density, medium-density, high-density, linear low-density various polyolefins such as polyethylene and polypropylene, ethylene vinyl acetate and the like Polyvinyl, acrylic such as ethylene ethyl acrylate and ethylene methyl acrylate,
Examples include rubbers such as styrene-butadiene, simple substances such as ionomers, blends, polymer polyamides, polyethylene terephthalate, polymethylpentene, and ethylene vinyl alcohol copolymer.

As the above-mentioned layer, two or more layers may be provided.

When these resins are laminated on a 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. Is mentioned.

The carbon black used in the present invention includes a furnace type, a channel type, an acetylene type,
It may be made by any method such as a thermal method.

Hereinafter, typical examples of the carbon black effective for the present invention will be described. Of course, it is not limited to these carbon blacks.

MA-600, manufactured by Mitsubishi Kasei Kogyo Co., Ltd., # 6
50B, # 40, # 3150, # 3250, # 3750, # 3950, MA-10
0, manufactured by CABOT, carbon VULCAN XC-72R, BLAC Pearl
s 700, manufactured by VULCAN P Lion Akzo Co., Ltd., Ketjen Black E.
C. Asahi Carbon Co., Ltd., Asahi HS-500 Other factors that affect the conductivity of carbon black include surface conditions (less impurities) and the progress of graphitization (commercially available). It is sufficient if it falls within the range specified above), which is an incidental performance. Basically, the oil absorption and the specific surface area are important items that determine the conductivity.

Usually, in order to produce a resin-processed light-shielding packaging material using carbon black, a so-called master in which carbon black is contained in a thermoplastic resin such as a polyethylene resin using a usual melt kneader such as a Banbury mixer kneader is used. Make a batch and dilute it with the diluted resin to the required ratio and adjust it, or adjust the so-called compound powder, which contains the required amount of carbon black in the resin from the beginning, or adjust the resin It is generally known to control the dispersion of carbon black in a dispersed latex liquid using a dispersant.

At this time, in addition to carbon black, a fatty acid metal salt such as zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, zirconium octylate, sodium barmitate, calcium palmitate, sodium laphrate and an antioxidant Can also be used.

The amount of carbon black required at this time differs depending on whether the resin is directly mixed into the resin or when the resin is mixed with a latex liquid in a state where the resin is dispersed.

That is, when directly mixed with the resin, the content is preferably in the range of 3 to 20% by weight, particularly preferably in the range of 5 to 15% by weight, based on the resin composition.

When mixed with a latex liquid, the content is preferably in the range of 10 to 40% by weight, and particularly preferably in the range of 15 to 30% by weight, based on the resin composition.

Means for processing the resin containing the light-shielding substance on the surface of the base paper include reverse roll method, blade method, air knife method, rod method, extrusion method, gravure roll method, dry lamination, wet lamination, and solution coating. It can be applied using a method such as the following.

Also, an adhesive layer may be used, and these known techniques can be used, and the present invention is not limited thereto.

[0040]

EXAMPLES The effects of the present invention will now be illustrated by examples.

Example 1 A base paper having the following grammage, smoothness, and sizing degree was prepared as the base paper for the light-shielding paper.

Sample No. Basis weight Smoothness (sec) Size degree (sec) Fog 1 75 60 15 × Comparison 2 75 60 10 × 〃 3 75 90 15 ○ Present invention 4 75 100 6 × Comparison 5 75 100 15 ○ The present invention 6 75 100 20 ○ 〃 7 75 120 6 × Comparison In papermaking of base paper, Kuraray Co., Ltd.
L118 was used.

A saturated polyester resin containing 8% by weight of carbon black (Vylore # 500, manufactured by Toyobo Co., Ltd.) was processed to a thickness of 20 μm in order to complete the light-shielding property on the back surface.

The following were used as the constitution of the ink used for the design printing on the surface.

Binder Ethylene vinyl acetate resin 1.0 part White pigment Titanium oxide (rutile type) 3.3 parts Solvent 4.0 parts Further, as a finishing varnish, 3.0 g / m ^{2 was} applied according to the following formulation.

Additives Polyethylene wax 2.0% by weight Resin Acrylic resin 30.0% by weight Solvent Toluol 18.0% by weight Solvent Isopropyl alcohol 50.0% by weight
X roll film, Konica Color 160S type was made. After putting this film in a moisture-proof bag and sealing it,
A storage test was performed for 3 days, and after the development processing using a common color developing solution, the fog occurrence was evaluated according to the following criteria.

：: No fog of the print pattern Δ: Fog of the print pattern is slightly observed on the negative film, but there is substantially no effect when printed. ×: Fog of the print pattern is clearly observed. Recognized and problematic when printed This result is noted in the fog column for the sample above.

As a result, it is understood that the sample of the present invention is hardly affected by the printing ink.

Example 2 The following inks were used as surface printing inks.

Sample No. Resin: Pigment Pigment: Titanium oxide (rutile type) a 1: 0.5 Resin: Polyacrylic resin b 1: 2.0 c 1: 3.0 d 1: 4.0 e 1: 5.0 Base paper of light-shielding paper used As the sample No. 2 of Example 1,
The same resin as in Examples 4 and 5 was used, and the same resin as in Example 1 was used as the finishing resin, and finished with the same coating amount. The contents are shown below.

Using these light-shielding papers, Konica Color SR8
0L 120 size packaged.

After being prepared and sealed in a moisture-proof bag,
After storage for one month, treatment and fog evaluation were performed in the same manner as in Example 1. The results are shown below.

Sample No. Ink used Base paper used Fog 11 a No. 2 ○ 12 b 〃 ○ 13 c 〃 △ 14 d 〃 〃 15 e 〃 × 16 a No. 4 ○ 17 b 〃 ○ 18 c 〃 △ 19 d 〃 × 20 e 〃 × 21 a No. 5 22 22 b 〃 23 23 c 〃 24 24 d 〃 25 25 e 〃 From these results, it can be seen that the sample of the present invention has no problem of print fog similarly to Example 1. Note that a 110-size film was prepared in place of the 120-size film, and a storage test was performed. The same result was obtained.

Example 3 Ink c of Example 2 was prepared using the following binder as a surface printing ink.

As the light-shielding paper used, sample No. 6 of Example 1 was used, and a 120-size film was prepared in the same manner as in Example 1 except for the above, and the storage fog was evaluated.

Sample No. Binder used Fog 31 Salt, vinyl acetate resin × 32 Polyester resin ○ 33 Styrene-maleic acid resin ○ 34 Polyester / urethane / ○ Acrylic ester resin From these results, chlorine resin was used. In this case, it is found that the photographic performance is adversely affected.

[0057]

According to the present invention, a light-shielding packaging material for a photographic light-sensitive material does not deteriorate the performance of the photographic light-sensitive material during storage over time without increasing the number of varnish coatings as in the prior art. A packaging material for photographic light-sensitive materials could be provided.

Claims (2)

(57) [Claims] 1. A packaging material for photographic photosensitive materials, 該写
Surface smoothness 65 to 130 DEG sec der true photosensitive material for packaging material
Ri, size of 7 to 20 se c of the packaging material for photographic photosensitive material, characterized in that paper is used. 2. A photographic photosensitive material according to claim 1, wherein the surface of the packaging material according to claim 1 is processed with an ink having a weight ratio of resin to pigment of 1: 0.5 to 1: 5 . Packaging material.