JPH1184597A - Photographic sensitive material assembly-wrapped body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a wrapped body, excellent in transparency, low-temp. heat sealability and suitability to high-speed wrapping and also low-cost-and excellent in suitability to recycling and incineration. SOLUTION: Plural photographic film cartridges separately housed in P cases are wrapped with a shrinkable film 7 in one body. The film 7 is a three- layered coextruded film of 20-70 μm thickness consisting of a intermediate layer 11, upper and lower layers 12 and 13. The intermediate layer 11 is a polyolefin resin layer having a high Young's modulus and contg. 0.2 pts.wt. calcium stearate, 0.05 pts.wt. hindered phenol antioxidant, 0.05 pts.wt. phosphorus antioxidant, 0.08 pts.wt. hydrotalcite compd., 0.1 pts.wt. dibenzylidene sorbitol type org. nucleating agent and 2 pts.wt. antistatic agent based on 100 pts.wt. echylene homopolymer resin. The upper and lower layers 12 and 13 are heat sealing layers contg. 40 pts.wt. ethylene homopolymer resin, 0.05 pts.wt. hindered phenol antioxidant, 0.05 pts.wt. phosphorus antioxidant, 0.05 pts.wt. erucic amide and 0.05 pts.wt. synthetic silica based on 100 pts.wt. ethylene.butene-1 copolymer resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photo-sensitive material assembly package for integrally packing a plurality of photo-sensitive material storage magazines represented by a photo film cartridge.

[0002]

2. Description of the Related Art Photosensitive materials such as photographic film and photographic paper are stored in a roll in a magazine called a patrone or a cartridge for easy handling. These magazines for storing photographic light-sensitive materials have slit-shaped outlets for drawing out and rewinding the photographic light-sensitive materials. Therefore, in order to ensure the moisture-proof property after production and before use, these photographic photosensitive material magazines are generally housed one by one in a moisture-proof case. For example, a popular 135-type photographic film is housed in a metal patrone, as is well known, and the patrone is housed in a cylindrical plastic moisture-proof case called a P case. Sold in small boxes.

In particular, since the 135-type photographic film is a commodity that is consumed in large quantities, a plurality of such photographic films are sometimes collectively packaged and sold. For example, JP-A-59-146848 describes a package in which a plurality of P-cased patrones housed in individually-packed small boxes are integrally packaged with a vinylidene chloride-coated biaxially stretched polypropylene resin film. I have. Further, Japanese Unexamined Patent Publication No.
Japanese Patent No. 122981 discloses a plurality of photographic photosensitive material storage magazines each housed in a cylindrical moisture-proof case.
A photographic light-sensitive material in which a heat-shrinkable film having a heat-shrinkage rate of 40 to 63% and a thickness of 35 to 50 μm and a heat-shrinkable film having a thickness of 35 to 50 μm when heated at 10 ° C. for 10 seconds is heat-shrinked to form an integrated package including a moisture-proof case. A collective package is disclosed.

[0004]

SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Application Laid-Open No. 59-14 / 1984
A collective package using a laminated film obtained by applying a vinylidene chloride resin layer to a biaxially oriented polypropylene resin film described in No. 6848 is excellent in transparency and excellent in low-temperature heat sealability, so high-speed packaging is also possible. The incinerator is damaged because it is expensive and generates chlorine gas during incineration,
There was a problem that plants and human bodies were harmed by incinerated chlorine gas. In addition, the single-layer film made of only the high-density polyethylene resin used in the invention described in JP-A-8-122981 has poor heat-sealing suitability (heat-sealing is not possible at high temperatures), has poor appearance, and is suitable for high-speed packaging. Is also lacking. Furthermore, because of cloudy resin film,
The appearance was poor, and it was difficult to prevent the occurrence of wrinkles and the like.

The present invention has been made in consideration of the above circumstances, and has excellent transparency, low-temperature sealability, high-speed packaging suitability, low cost, and does not adversely affect the photographic properties of photographic photosensitive materials. An object of the present invention is to provide an excellent photographic light-sensitive material assembly package.

[0006]

In order to achieve the above object, a photographic photosensitive material assembly package of the present invention comprises a plurality of photographic photosensitive material storage magazines each stored in a moisture-proof case.
A heat-sealing layer composed of only a polyolefin resin layer having an ethylene-based resin layer containing 5% by weight or more of a low-density homopolyethylene resin and / or an ethylene copolymer resin and having a thickness of 20 to 70 μm and a monoaxially stretched multilayer laminated film having a thickness of 20 to 70 μm. It is a sleeve package. The value of the ethylene-based resin layer measured by ASTM D638 is 6%.
This is a single-layered, vertically uniaxially stretched multilayer film having a thickness of 20 to 70 μm provided on both sides of a high Young's modulus polyolefin resin layer of 000 kgf / cm ² or more.

The heat sealing layer has a density of 0.
5 to 99.989% by weight of ethylene-α-olefin copolymer resin of 870 to 0.935 g / cm 3, lubricant 0.01
10 to 10% by weight, and 0.001 to 1% by weight of a phenolic antioxidant and / or a phosphorus antioxidant. A single uniaxially stretched multilayer film having a thickness of 20 to 70 μm and provided with a high Young's modulus polyolefin resin layer having a value of 6000 kgf / cm ² or more measured by ASTM D638 on the outside of the heat seal layer and integrally sleeve-wrapped. It is.

Further, the photographic photosensitive material assembly package is stored in a moisture-proof bag with printing. Further, the photographic light-sensitive material assembly package is housed in an easy-opening decorative box made of coated printing paper having a coating layer on at least the printing surface side of two or more laminated paperboards. Further, the surface of the easy-opening decorative box is processed in the order of a coating layer, a printing layer, and an overprint varnish from the surface side of two or more laminated paperboards.

The vertically uniaxially stretched multi-layer laminated film is formed by uniaxially stretching a multi-layer co-extruded film of two or more layers only in the longitudinal direction (for example, by heating between a frontmost driving roll and a rearmost driving roll, a plurality of films capable of free rotation). Are rolled, and a film is passed between them, and the film is stretched to a predetermined magnification by a difference in rotation speed between two driving rolls). First, a longitudinally uniaxially stretched polyolefin resin film (density of various polypropylene resin films and Is 0.940 g / cm
³ or more of various types of polyethylene resin films are preferable), and a low-density homopolyethylene resin film and / or an ethylene copolymer resin containing 5% by weight or more of a low-density homopolyethylene resin film as a heat seal layer on at least one surface of the longitudinally uniaxially stretched polyolefin resin film. A multi-layer laminated film in which the resin layer is provided as a melt-extruded coating layer, or a multi-layer laminated film in which the above specific heat seal layer is provided as a melt-extruded coating layer on at least one surface of a longitudinally uniaxially stretched polyolefin resin film manufactured in a separate process. It may be a film.

As a packaging machine used for sleeve packaging, a fixed seal type sleeve packaging machine, a traveling seal type sleeve packaging machine, a sleeve packaging machine containing cut tape, and a tight sleeve packaging machine are known. The fixed seal type sleeve packaging machine is a packaging type mainly used as a set with a shrink tunnel. Hang it on a screen, seal the upper and lower laminated films with an integral seal bar, and connect them. When the product is sent into it and the laminated film is sealed and cut with a seal bar at the back of the product, a sleeve (sleeve) package with both sides of the product open can be formed. The laminated film on both sides shrinks to form a circular window, enabling tight packaging. The packing capacity is 5 to 20 packs / min, depending on conditions such as the size of the product.

When the packing capacity is 25 to 30 packs / min, the fixed seal type cannot cope with the problem, so that the seal bar has a function of running at the same speed as the front and rear conveyor belts, and the rear end of the product is provided with the seal bar. At the time of passing, the seal bar is run at the same speed as the conveyor, and a running seal type sleeve packaging machine for sealing and cutting the laminated film behind the product is used.

In general, a sleeve packaging machine containing a cut tape supplies approximately the same amount of laminated film from above and below and seals it with a seal bar. When the product is positively unwound from 10 to 15 mm for one product, and then the product is covered and sealed with the upper laminated film, 2
The seal lines of the book are close to each other, and can serve as a cut tape. In particular, the effect is remarkable when the lower laminated film is contracted by using a laminated film thicker than the upper laminated film and further using a laminated film wider than the upper laminated film.

The tight-sleeve wrapping machine is designed to pull back the laminated film when the product is fed into the laminated film and seal it, and to cut the laminated film tightly with respect to the product. In this method, since the laminated film itself can have a binding force to the product, a contraction tunnel in a post-process is not required at all.

FIG. 3 shows a state in which a photographic film cartridge 3 is accommodated in a P case 2 used as a moisture-proof case. The photo film patrone 3 has a winding shaft 3b rotatably housed in a metal patrone main body 3a, and the photographic film is wound around the winding shaft 3b in a roll shape. P case 2
Consists of a bottomed cylindrical case body 4 and a cap 5, each of which is an integrally molded product of plastic. P
Case 2 is a photo film cartridge 3 stored in it.
Protects the unit from moisture, dust and compressive loads. When the photo film patrone 3 is put in the case body 4 and the cap 5 is put on the case body 5, the projection 5a of the cap 5 is
The photo film cartridge 3 is sealed in the P case 2.

FIG. 4 shows a photo film cartridge containing 5 cartridges.
A collective package 1 in which P cases 2 are collectively packaged with a laminated heat-shrinkable film 7 having perforations (hereinafter referred to as a shrink film) 7 is shown. The P case 2 is arranged such that the caps 5 are alternately arranged on the top and bottom sides, and is tightly packaged by a laminated shrink film 7 having heat-shrinkable perforations. Note that, depending on the packaging form, the cap 5 may be aligned with one of the top and bottom.

The lamination type shrink film 7 is provided with perforations 8 so as to be located at the boundary between the P cases 2.
Is given. Then, by breaking the laminated shrink film 7 along the perforations 8 immediately before use, only one P case 2 can be taken out. The tensile strength of this perforation 8 is 500 to 630 (g
(f / 15 mm width), the perforations 7a are not easily broken by the vibration when transporting the collective package 1 or the impact when dropped, and the originality and the openability are maintained. . In this example, since two laminated shrink films 7 having perforations are formed, seams 9 formed by heat sealing the respective laminated shrink films 7 are formed on the top and bottom of the collective package 1.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION A laminated shrink film (hereinafter simply referred to as a shrink film) 7 is a three-layer co-extruded film having the following composition, and the thickness of each layer and the total thickness are changed. Reference Examples 1-3, Conventional Example 1
3 to 3, heat shrinkage, drop strength, transparency, suitability for sleeve packaging, appearance, suitability for low-temperature heat seal, suitability for heat seal over time, antistatic properties, suitability for putting in and taking out moisture-proof bags, suitability for putting in and out of cosmetic boxes, photographing (collective packaging ) (Photosensitive material (laminated film) directly sealed and packaged), suitability for incineration, and film moldability were evaluated, and the following Table 1 was obtained.
The evaluation symbols ◎, ○, ●, ▲, × in the table indicate “very good”, “excellent”, “practical limit”, “improvement required”, and “practical difficulty”, respectively. ing.

The measuring methods A to N in the table are as follows. The measurement method A of the heat shrinkage rate is 5c for each sample.
After marking a square of mx 5 cm and immersing the sample in a glycerin bath set at a temperature of 140 ° C for 10 seconds, the difference ΔL between the vertical and horizontal dimensions of the square before heating and the square after heating was determined, and the heat shrinkage rate ( %) = (ΔL / 5) × 100.

In the method B for measuring the drop strength, each sample in which five P cases are collectively packaged is measured in accordance with JISZ0200 "Appropriate packaged cargo test method". The transparency measuring method C is a method of measuring and evaluating according to ASTM D1003. The measuring method D of the suitability for sleeve packaging is as shown in Table 2 described later. The appearance measurement method E is based on the value obtained by counting the number of wrinkles that appeared on the surface of the collective package after shrink packaging, dividing the total number by the surface area, and converting the total number to the number of wrinkles per unit area.

The method of measuring suitability for low-temperature heat sealing F is to measure and evaluate a temperature at which a sheet seal strength of 0.5 kg / 15 mm width can be secured when two shrink films are stacked and heat-sealed. The lower the rating, the better.) Method for measuring heat sealability over time G
When two sheets of shrink film (15 mm width) are overlapped and heat-sealed, sealing is performed at a temperature at which the seal strength is maximized, at a seal pressure of 1 kg / cm ² and a heat time of 1.5 seconds, and required for peeling after cooling. The load is determined, the load required for peeling is determined after one month from the heat-sealing, and the reduction rate of the heat-sealing strength (load) is measured and evaluated (the smaller the reduction rate, the better). And evaluation).

The measuring method H of the antistatic property is based on JIS K69.
This is measured and evaluated according to No. 11. As shown in FIG. 5, the method I for measuring the suitability for putting in and taking out the moisture-proof bag is as shown in FIG. (Easier is better). The measuring method J of suitability for putting in and taking out the cosmetic box is evaluated from the ease of putting the collective package 1 in and out of the easy-opening decorative box 42 shown in FIG. Easier ones are better).

The photographic property (assembled package) K is measured by using Fujicolor Super G400 (trade name) and developing after shrink wrapping to measure the fog density _Dmin in blue where fogging is most likely to occur. Was evaluated. The determination of the fog density was compared with the fog density standard D _min = 9.0 ± 0.02 of the same type of photographic film without shrink wrapping.

The measurement method L for photographic properties (photosensitive material (laminated film) is directly sealed and packaged) is Fujicolor Super G
400 (trade name) is directly sealed and packaged with a shrink film, and then developed to measure and evaluate the fog density _Dmin in blue where fog is most likely to appear. Evaluation of fog density is compared with blank.

The method M for measuring the suitability for incineration is evaluated based on the possibility of incineration and the presence / absence of toxic gas during incineration. The method N for measuring film formability is a comprehensive evaluation of film formability, such as the occurrence of melt fracture, wrinkles, streaks, etc., extrudability, and productivity during film formation.

[0025]

[Table 1]

[Examples 1 to 6] In FIG.
1 is a density of 0.956 g / cm ³ , MFR 0.05 g /
Homopolyethylene resin 100 having a molecular weight distribution of 25 for 10 minutes
0.2 parts by weight of calcium stearate,
0.05 parts by weight of a hindered phenol-based antioxidant, 0.05 parts by weight of a phosphorus-based antioxidant, 0.08 parts by weight of a hydrotalcite compound, a dibenzylidene sorbitol-based organic nucleating agent (manufactured by Shin Nippon Rika Co., Ltd.) Gerol MD) 0.1
It is a high Young's modulus polyolefin (PO) resin layer containing 2 parts by weight of an antistatic agent masterbatch (Erestmaster HE-510 manufactured by Kao Corporation).

The upper and lower layers 12 and 13 have a density of 0.920 g /
cm ³ , MFR 2.1 g / 10 min, 100 parts by weight of ethylene / butene-1 copolymer resin having a molecular weight distribution of 3.5, density 0.918 g / cm ³ , MFR 1.2 g / 10
40 parts by weight of a homopolyethylene resin having a molecular weight distribution of 7.7, 0.05 parts by weight of a hindered phenol-based antioxidant, 0.05 parts by weight of a phosphorus-based antioxidant, 0.05 parts by weight of erucamide, synthetic silica An ethylene resin layer and a heat seal layer (= ethylene resin layer) containing 0.05 parts by weight.

Alternatively, the intermediate layer 11 may be manufactured in a separate step and sandwiched by a melt-extruded ethylene resin layer (heat seal layer). Example 6 uses a two-layer coextrusion film 15 as shown in FIG.

[Comparative Examples 1 to 3] Intermediate layer 1 of Examples 1 to 6
This is a single-layer, vertically uniaxially stretched, high Young's modulus polyolefin resin film having the same resin composition as 1.

[Conventional Example 1] This is the invention A (biaxially stretched homopolypropylene resin film coated on both sides with polyvinylidene chloride) described in JP-A-59-146848. [Conventional Example 2] Conventional Example D (unstretched polyethylene film) described in JP-A-59-146848. [Conventional Example 3] This is Sample H described in JP-A-8-122981.

The sleeve packaging conditions are shown in Table 2 below. The temperature in the tunnel of the vertically uniaxially stretched laminated film is 120 to 190 ° C, preferably 125 to 185 ° C.
More preferably 130 to 180 ° C, particularly preferably 13 to 180 ° C.
5 to 175 ° C, most preferably 135 to 170 ° C. The heating time is 5 to 20 seconds, preferably 6 to 18 seconds, more preferably 7 to 16 seconds, particularly preferably 8 to 15 seconds,
Most preferably, it is 9 to 14 seconds.

[0032]

[Table 2]

As shown in FIG. 5, the collective package can be placed in a moisture-proof bag 28 for further improving the moisture-proof property.
A hole 28a is formed in the packaging bag 28 in which the collective package 26 is stored so that the package 28 can be hung on a hanger display for display. The operation of sealing the collective package 26 in the packaging bag 28 is performed by an automatic packaging machine (manual work is also possible).
Therefore, the packaging process is simplified as compared with packaging a plurality of P cases 2 individually, and the automatic packaging efficiency can be significantly improved.

As shown in FIG. 6, the layer structure of the packaging bag 28 is such that the EVA (ethylene vinyl alcohol) layer 30 is 40
μm, the PE (polyethylene) layer 31 has a thickness of 20 μm, the aluminum foil 32 has a thickness of 7 μm, the PE layer 33 has a thickness of 15 μm, and the polyester film layer has a thickness of 12 μm.
The anchor coats 35 and 36 are respectively provided on the inner side of the PE layer 33 and the outer side of the PE layer 33, and a printed layer 37 such as a product name or a manufacturer name is provided on the surface of the anchor coat 36. The layer configuration of the packaging bag 28 is not limited to the above,
Various moisture-proof packaging bags can be used as long as the moisture-proof property is secured by the moisture-proof case and the originality is secured by the shrink film having perforations, so long as the commercial value in appearance can be improved.

Next, the middle layer 11 is the same and the upper and lower layers 12, 1
Table 3 shows the results of preparing Examples A to F in which the composition of Example 3 was changed and measuring the suitability for packaging. The upper and lower layers 12, 1
3 has a density of 0.902 g / cm ³ and an MFR of 2.0
g / 10 min, ethylene and gas phase polymerization using metallocene catalysts of the molecular weight distribution 2.0 - hexene 1 copolymer resin density 0.920g / cm ^3, MFR2.1g / 10 min,
Except for using the ethylene / butene-1 copolymer resin having a molecular weight distribution of 3.5, the same resin composition as in Examples 1 to 6 was used.

Examples F and G are packages using a shrink film having the same resin composition and the same layer structure as those of Example B. Example G was a case where the P case was square, and a photographic light-sensitive material assembly package having more excellent packaging suitability and appearance than a cylindrical case was obtained. Example H was a case where the P case was oval (both with one photographic film and two photographic films), which was inferior in packaging suitability to the case of a cylindrical shape, but was in a practically feasible range.

[0037]

[Table 3]

As can be seen from Tables 1 and 3, Examples 1 to 6, A to F, G and H of the present invention have higher drop strength than Comparative Examples 1 to 3 and Conventional Examples 1 to 3. , Improved transparency,
Improved sleep packaging suitability, improved appearance (no wrinkles or streaks), excellent low-temperature seal suitability, no reduction in heat seal strength over time, improved moisture-proof bag and makeup box insertion and removal, good photographic properties, It was also found that it had excellent suitability for incineration and recycling. That is, 5% by weight of an ethylene copolymer resin is added to both sides of the high Young's modulus polyolefin resin layer.
By forming a laminated film comprising a multilayer co-extruded film having a polyethylene resin layer containing a lubricant and a lubricant as described above, the film formability can be improved, the suitability for packaging can be improved, and the low-temperature heat-sealing property and heat-sealing property over time can be excellent. It has been found that a photographic photosensitive material assembly package can be provided.

The heat seal layer has an ultra low density (density 0.90
In Examples A to F of the present invention using an ethylene-hexene 1 copolymer resin polymerized using a metallocene catalyst (less than 9 g / cm @ 3), the drop strength, transparency, and low-temperature heat sealing suitability of a conventional Ziegler catalyst were used. Ethylene polymerized
Examples 1-6 of the invention using butene-1 copolymer resin
Even better.

With respect to the high-density polyethylene used for molding the P case, Examples A to F shown in the following Table 4 were used.
Experiments were conducted using comparative examples A to D. MFR ｛(AS
Measured under the E condition of TMD1238 (temperature: 190 ° C., piston load: 2.16 kg): 22 g / 10 min, molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn measured by GPC method): 3.8, density (Measured by ASTM D1505) is 0.972 g / cm ³ , and Olsen rigidity (ASTM)
D747) (measured by ASTM D256), 13500 kg / cm ² , 23 ° C. Izod impact strength (measured by ASTM D256).
5 kg / cm / cm, Shore hardness (ASTMD2240
Is 65D, Vicat softening point (ASTMD152)
5, the melting point (measured by ASTM D2117) is 131 ° C., and the crystallinity (measured by the X-ray diffraction method) is 94.
% Of high-density polyethylene resin (content of α-olefin other than ethylene is 0.1 mol% or less) per 100 parts by weight of oleamide 0.05 part by weight, calcium stearate 0.1 part by weight, phosphorus-based antioxidant 0.05 parts by weight,
0.05 parts by weight of hindered phenolic antioxidant, dibenzylidene sorbet organic nucleating agent (Shin Nippon Rika KK
Resin composition (a) obtained by mixing 0.1 parts by weight of Gelol MD manufactured by Kabushiki Kaisha, 0.08 parts by weight of hydrotalcite, and 2 parts by weight of an antistatic master batch (trade name: Erestmaster HE-10) manufactured by Kao KK Single screw extruder
5mmφ, L / P is 32), resin temperature 220 ° C,
Melt and knead under the conditions of a screw rotation speed of 80 rpm and 20
The udon-shaped stride was extruded into cold water at ℃, cooled with water, and then cut into a columnar shape having a length of 3.5 mm using a pelletizer. The diameter l of the die used was 3.5 mmφ
It is. The take-up speed of the pelletizer was adjusted so that the diameter of the strand ls / the diameter of the die 1 became the value shown in Table 4. For the same reason as in Examples 1 to 5, the strand diameter l
s measured and displayed the diameter of the pellet. A hot runner type mold having 24 cavities at a resin temperature of 210 ° C. using the pellets is used, and the injection molding machine is a toggle-type clamping device with a mold clamping pressure of 150 t (Sumitomo Heavy Industries K
An 8 second cycle de-injection molding was carried out using K (trade name of Nestal). Table 4 shows the results. In Example F, although the resin composition was the same, an almost spherical pellet (about 3.5 mm in diameter) of an underwater hot cut method was used.

In Comparative Examples C and D, 0.1 to 0 parts by weight of calcium stearate, 0.05 to 0 parts by weight of oleic amide, and antistatic agent masterbatch 2 to 0 parts by weight of the resin composition A were used.
The resin composition (b) changed to parts by weight was used.

[0042]

[Table 4]

Representative examples of various ethylene copolymer resins preferably contained in the heat seal layer are shown below. (1) Ethylene-vinyl acetate copolymer (hereinafter "EVA")
Resin) (2) ethylene-propylene copolymer resin (3) ethylene-1-butene copolymer resin (4) ethylene-butadiene copolymer resin (5) ethylene-vinyl chloride copolymer resin (6) ethylene -Methyl methacrylate copolymer (hereinafter, referred to as
(7) Ethylene-methyl acrylate copolymer (hereinafter referred to as “E
MA) (8) Ethylene-ethyl acrylate copolymer (hereinafter referred to as “E
EA ") resin (9) Ethylene-acrylonitrile copolymer resin (10) Ethylene-acrylic acid copolymer (hereinafter" EAA ")
(11) ionomer resin (resin obtained by crosslinking a copolymer of ethylene and an unsaturated acid with a metal such as zinc) (12) ethylene-α-olefin copolymerization (hereinafter referred to as “L-LD”)
("PE") resin (13) Ethylene-propylene-butene-1 ternary copolymer resin, etc.

A particularly preferred ethylene copolymer resin for the heat seal layer of the present invention is L-LDPE resin.
The reason is that the photographic properties of the photographic light-sensitive material are not adversely affected, the suitability for low-temperature heat sealing, the heat-sealing strength maintaining property over time, the physical strength are excellent, the polymerization energy is low, and the cost is low. Details of the L-LDPE resin are shown below.

L-LDPE (Linear Low D)
(Energy Polyethylene) resin is referred to as a third polyethylene resin, and has a medium / low density, a high density,
It is a low-cost, high-strength resin that meets the era of energy and resource savings combining the advantages of both polyethylene resins. This resin is a copolymer of ethylene and an α-olefin having 3 to 20, preferably 3 to 13, more preferably 4 to 10, and particularly preferably 5 to 9 carbon atoms. Is a polyethylene resin having a short branch structure. Preferred α-olefins in terms of physical strength and cost include, for example, propylene, butene-1, pentene-1, octene-1, hexene-1, 4-methyl-
Pentene-1, heptene-1, 3-methyl-pentene-
1,4,4-dimethyl-pentene-1, nonene-1, undecene-1, dodecene-1, decene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, and the like are used. In the present invention, the α-olefin is preferably butene-1, hexene-1, pentene-1,4-methyl-pentene-1, and octene-1 because the physical strength, heat sealing suitability and photographic properties are excellent. And the content of these α-olefins is 0.05 to 3
5 mol%, preferably 0.1 to 25 mol%, more preferably 0.5 to 15 mol% L-LDPE resin, most preferably 1 to 8 mol% L-LDPE resin.

Specific examples of commercially available L-LDPE resins produced by polymerization using a conventional Ziegler catalyst are shown below. Ethylene butene-1 copolymer resin: G resin and NUC-FLX (UCC
Co., Ltd.), Dourex (Dow Chemical), Scrair (DuPont Canada), Marlex (Philips), Stamirex (DSM), Excellen VL
(Sumitomo Chemical), Neozex (Mitsui Petrochemical), Yucaron-LL (Mitsubishi Yuka), Nisseki Linirex (Nippon Petrochemical), NUC Polyethylene-LL (Nippon Unicar), Nipolon L (Tosoh), Shorex Linear (Showa Linear) Denko), Ube Polyethylene L (Ube Industries), Idemitsu Polyethylene L (Idemitsu Petrochemical), etc., ethylene / hexene-1 copolymer resin: TUFLIN (UCC), TUFTHEN
E (Nihon Unicar), etc., ethylene 4-methylpentene
1 Copolymer resin: Ultzex (Mitsui Petrochemical), etc., ethylene / octene-1 copolymer resin: Stamilex (D
SM), Dourex (Dow Chemical), Screa (DuPont Canada), MORETEC (Idemitsu Petrochemical) and the like.

Balun for improving physical strength and film formability
Particularly preferred from the point of view of MFR (ASTM D-
E condition of 1238-88, temperature 190 ° C, test load
2.16 kgf) 0.05 to 20 g / 10 min,
Preferably 0.1 to 15 g / 10 min, more preferably
0.2-8 g / 10 min, most preferably 0.5-5 g /
10 minutes, density (measured by JIS K-6760) is 0.8
70-0.940 g / cm ^Three, Preferably 0.880-
0.935g / cm^Three, More preferably 0.890-
0.928 g / 10 min, most preferably 0.900 to
0.920 g / 10 min, and carbon number of α-olefin
Is 3 to 12 random-type L-LDPE resins
You.

The polymerization catalyst residue is small, the adverse effect on the photographic properties of the photographic light-sensitive material is small, the rust of the mold and the extruder during film forming is small, and the low-temperature heat sealability, physical strength, etc. are the above-mentioned Ziegler catalysts. The most preferred as the ethylene copolymer resin for the heat seal layer of the present invention is L-LDPE produced by polymerization using the following single-site catalyst, since it is more excellent than L-LDPE resin using
Resin.

In the present invention, the term "single-site catalyst" refers to a catalyst having a uniform active site different from a conventional "multi-site catalyst" having non-uniform active site properties, and has substantially the same molecular weight (molecular weight). (Narrow distribution and composition distribution). In particular, in the case of a copolymer resin, when manufactured using the “single-site catalyst” of the present invention, comonomers are evenly inserted into any molecular weight component, resulting in a thermoplastic resin having a small (narrow) molecular weight distribution and composition distribution. It has heat sealing properties, good photographic properties, high physical strength, and excellent transparency and anti-blocking properties. For the laminated film application of the present invention, an ethylene-α-olefin (having 3 to 12 carbon atoms) random copolymer resin is most preferred.

A typical single site catalyst is 1
A catalyst discovered by Professor Kaminsky of Hamburg University in 980 as a highly active polymerization catalyst for polyethylene resins. In general, the catalyst is soluble in an organic solvent and has a single kind of catalytically active site. A typical polymerization method of L-LDPE resin using the metallocene catalyst is disclosed in the following gazettes, but the present invention is not limited thereto. JP-A-58-1
9309, JP-A-60-862, JP-A-6
0-35006, JP-A-60-35007, JP-A-60-35008, JP-A-60-10
No. 6008, JP-A-61-296008, JP-A-63-28070, JP-A-1-95110 and the like.

Representative examples of commercially available products are described below, but the present invention is not limited to these. A typical example of ethylene resin (mostly L-LDPE resin) is Exxon's "EXAC" as a high pressure ion polymerization method.
T, Mitsubishi Chemical's Kernel, Tosoh's Catal
lotene ”, and“ AFFINITY ”and“ ENG ”of Dow Chemical Co., Ltd.
AGE "and the like. As the gas phase polymerization method, there is "EVOLUE" (Mitsui Petrochemical). In the present invention, the molecular weight distribution (weight-average molecular weight Mw / number-average molecular weight Mn) measured by the GPC method produced by polymerization using a single-site catalyst in the thermoplastic resin is 1.1 to 1.1.
10, preferably 1.2 to 7, particularly preferably 1.3 to
5 is an L-LDPE resin. The density is 0.870 to 0.925 g / cm in terms of low-temperature heat sealability and physical strength.
³ , preferably 0.880 to 0.920 g / cm ³ , more preferably 0.890 to 0.915 g / 10 min, particularly preferably 0.900 to 0.910 g / 10 min LL
DPE resin.

When used in combination with the above-mentioned ethylene / α-olefin copolymer resin, physical strength is excellent, film formability is good, heat seal strength is large, and rust and corrosion of an extruder or a film forming machine are involved. As the resin for the heat seal layer of the present invention, which is inexpensive and does not contain a catalyst residue that adversely affects the photographic properties of the photographic light-sensitive material, the next preferred resin after the L-LDPE resin is a low-density homopolyethylene resin (hereinafter LDP).
E resin).

The following is a list of commercially available LDPE resin manufacturers and trade names.

[0054]

[Table 5]

Among these LDPE resins, MFR (AS
(Measured at a temperature of 190 ° C. and a test load of 2.16 kgf under the condition E of TM D-1238-88) is 0.05 to 20 g / 1.
0 min, preferably 0.1-15 g / 10 min, more preferably 0.2-8 g / 10 min, most preferably 0.5-5 g / 10 min.
g / 10 minutes, density (JISK-6760 or ASTM
0.910 to 0.925 g / cm)
3, preferably 0.912 to 0.923 g / cm3, more preferably 0.915 to 0.921 g / cm3.

The content of the L-LDPE resin and / or LDPE resin in the heat seal layer is at least 5% by weight, preferably at least 10% by weight, more preferably at least 10% by weight in view of heat seal strength, low temperature heat sealability, heat seal suitability and the like. It is at least 20% by weight, particularly preferably at least 50% by weight, most preferably at least 70% by weight.

The thickness of the vertically uniaxially stretched multilayer laminated film is 2
0 to 70 μm, preferably 25 to 65 μm, more preferably 30 to 60 μm, particularly preferably 30 to 55 μm,
Most preferably, it is 30 to 50 μm. If it is less than 20 μm, the physical strength is insufficient.

The longitudinal uniaxial stretching ratio is 1.5 to 20 times, preferably 2 to 15 times, more preferably 2.5 to 10 times, and particularly preferably 3 to 8 times. If it is less than 1.5 times, the heat shrinkage rate is small, the collective package is loose, the appearance and the original sealing property are deteriorated, and it becomes difficult to open even if perforated. On the other hand, when the ratio exceeds 20 times, wrinkles and streaks are generated in the collective package, and furthermore, vertical tearing is more likely to occur, which makes practical use difficult.

The heat shrinkage is 30 to 70%, preferably 3
It is 5 to 65%, particularly preferably 40 to 60%. 30
%, The assembled package becomes loose, and the appearance and the original sealing property are deteriorated. If it exceeds 70%, wrinkles and streaks are generated in the collective package, which makes practical use difficult.

In the present invention, a high Young's modulus (ASTM D638) is used.
Means a value of 6000 kgf / cm ² or more, preferably 6500 kgf / cm ² or more, more preferably 7000 kgf / cm ² or more, and particularly preferably 7 or more.
500 kgf / cm ² or more, most preferably 8000 k
gf / cm ² or more.

The laminated film for a moisture-proof bag according to the present invention is
Condition B of Z-0208 (cup method) (temperature 40 ± 0.
5 ° C., relative temperature 90 ± 2 ° C., the present invention has a moisture permeability of 10 g / m ² · 24 hours or less, preferably 7 g / m ² · 24 hours or less, particularly preferably 5 g / m 2/24 hours or less.
m ² · 24 hours or less, most preferably 3 g / m ² · 24
Less than an hour. Representative examples usable in the present invention are described below, but the present invention is not limited to these.

[0062] -1 (for a thickness of 100 [mu] m) the single plastic film moistureproof cellophane 9.2 g / m ² · 24 hours biaxially oriented polyethylene terephthalate resin film 5.4 g / m ² · 24 hours rigid polyvinyl chloride resin film 5.2 g / m ² · 24 hours density 0.920 g / cm ³ of homopolyethylene resin film 4.9 g / m ² · 24 hours density 0.960 g / cm ³ of homopolyethylene resin film 4.9 g / m ² · 24 hours undrawn homo crunching sound-plane resin film 3.0 g / m ² · 24 hours biaxially oriented homopolymer crunching sound-plane resin film 1.1 g / m ² · 24 h 2 (case of a thickness of 25 [mu] m) the single plastic film biaxially oriented homopolymer crunching sound-plane resin film 5.5 g / m ²・ 24 hours uniaxially stretched high density polyethylene resin film 6.5 g / m ²・ 24 hours biaxially stretched polyethylene naphthalate resin film (PEN) 7.0 g / m ²・ 24 hours biaxially stretched polyethylene terephthalate Resin film ^{(PET) 6.0 g / m 2} · 24 hr -3 monolayer plastic film thickness and the moisture permeability (g / m ² · 24 hr) Film thickness (μm) 20 25 30 40 60 80 100 unstretched homopolypropylene resin film - 10 9 7 5 4 3 density 0.935 g / cm ³ of L-LDPE resin film - - 14 10 7 6 5 density 0.920 g / cm ³ of L-LDPE resin film - - - 14 10 8 7 biaxial stretching homo polypropylene-plane resin film 7 5 3 - - - - -4 vinylidene coated plastic film of vinylidene chloride-coated OPP film chloride (thickness 20μm) 3g / m ² · 24 hours (abbreviation KOP) vinylidene chloride coated PET film (thickness 12 [mu] m) 7g / m ² · 24 hours (abbreviation KPET) vinylidene coated ONY film (thickness 15 [mu] m) chloride 9g / m ² · 24 hours (abbreviation kony) vinylidene chloride-coated vinylon film (thickness 20μm) 4g / m ² · 24 hours ( abbreviations K vinylon) vinylidene coated cellophane film (thickness 20μm chloride) 10g / m ² · ² 4 hours (abbreviation: K cellophane) -5 Aluminum vacuum-deposited plastic film Aluminum (denoted as AL) Deposited film thickness (Å) and change in moisture permeability depending on the type of film used are shown in Table 6 below. In addition, the cup method (condition B of JIS Z-0208) is used as the measuring method.

[0063]

[Table 6]

In Table 6, when the deposited film thickness is 200 ° or more, each resin film shows good moisture permeability. However, when the deposited film thickness is 0 ° where no aluminum deposition is performed, the resin film has good permeability. The extreme increase in the value of humidity indicates that aluminum deposition is a very effective means for improving the moisture-proof properties.

Next, for various aluminum-deposited resin films, the aluminum-deposited film thickness and oxygen gas permeability (c
c / m ² · 24 hours · 20 ° C.) are shown in Table 7. Note that the measuring method uses the MOCON method (same pressure method).

[0066]

[Table 7]

In Table 7, the oxygen gas permeability is high when the vapor deposition film thickness is 200 ° or less, but the oxygen gas permeability decreases as the aluminum vapor deposition film thickness increases. It turns out that it is effective in preventing permeation of oxygen gas.

-6 Moisture Permeability (Condition B of JIS Z-0208) and Number of Pinholes Aluminum Foil Thickness (μm) 6 7 8 9 10 12 15 20 25 Moisture Permeability (g / m ² · 24 hours) ) 3.3 2.4 1.9 1.6 1.2 0.7 0.4 0.1 0 Number of pinholes (pieces / m ² ) 230 36 18 9 5 3 2 1 0 -7 Inorganic oxide [alumina, silicon oxide (SiOx), etc.] Thin film deposition film [Laminated structure] [JIS Z-0208 moisture permeability was measured under the conditions B of] PET (12μm) / SiOx deposition film ^{/ AD (4g / m 2)} / CPP (70 μm) 0.6g / m 2 · 24 h PET (12μm) / SiOx Evaporated thin film / AD (4g / m ² ) / L-LDPE (40μm) 0.8g / m ²・ 24 hours OPP (20μm) / SiOx Evaporated thin film / AD (4g / m ² ) / CPP (40μm) 0.2g / m ²・ 24 hours The characteristics of these inorganic oxide thin film deposition films are transparency,
This film is excellent in moisture proof, more resistant to acid and alkali than aluminum foil, and is environmentally friendly. It can be burned without any problem, no residue remains in the combustion furnace, and it does not damage the incinerator. Representative commercial products and manufacturers of this inorganic oxide thin film deposition film are described below. MOS (Oike Industry KK) BARRIALOX (Toyo Metallizing K
K) Tech Barrier (Mitsubishi Chemical KK) Fine Barrier P-11 (KK Reiko)

The moisture permeability of the laminated film [the adhesive layer is a dry laminate adhesive layer (urethane-based 2 g / m ² )] [Laminated film] [Moisture permeability] ONY 15 μm / PVDC 15 μm / CPP50 μm 0.9 g / m ² .24 hours ONY 15 μm / PVDC 15μm / L-LDPE 60μm 0.9g / m 2 · 24 hours PET 12μm / PVDC 15μm / L- LDPE 50μm 0.9g / m 2 · 24 hours PET 12 [mu] m / stretching EVOH15μm / L-LDPE 50μm 2.2g / m 2 · 24 hours PET 12 [mu] m / aluminum vapor deposition (400Å) OPP20μm / CPP25μm 0.5g / m 2 · 24 hours

[0070] Various bonding article vapor permeability OPP (20μm) / PE (40μm ) 4~ 6g / m 2 · 24 h ON (15μm) / PE (40μm ) 15~20g / m 2 · 24 hours OPP (20 [mu] m ) / Aluminum evaporated PE (30 μm) 2 to 4 g / m ²・ 24 hours PET (12 μm) / Aluminum foil (7 μm) / PE (20 μm) 0 to 1 g / m ²・ 24 hours PET (12 μm) / Aluminum foil (9μm) / CPP (70μm) 0g / m 2 · 24 hours paper / PE (15μm) / aluminum foil (7μm) / PE (20 μm ) 0~ 1g / m 2 · 24 h PET (12μm) / PE (15 μm) / aluminum foil (7 μm) / PE (30 μm) 0-1 g / m ² · 24 hours OPP: stretched polypropylene, PE: polyethylene, ON: stretched nylon, PET: stretched polyester.

Representative examples of the structure of the laminated film are shown below. Cellophane / AC / AD / PO Paper / AD / PO OPP / AD / PO OPP / AC / AD / PO OPP / AC / EL PO KOP / AC / EL PO KOP / AC / AD / PO Coextrusion OPP / AC / AD / PO PET / AC / AD / PO K PET / AC / AD / PO CPP / AC / AD / PO NO-NY / AC / AD / PO O-NY / AC / AD / PO KON / AC / AD / PO EVOH / AC / AD / PO Uniaxially stretched PO / AC / AD / PO PS / AC / AD / PO K cellophane / AC / AD / K cellophane / ELPO K cellophane / AC / AD / glassine paper / ELPO PET / AD / AL / AD / PO PET / AD / PET / AD / PO PET / AD / ONY / AD / PO PET / AD / CPP Co-extrusion OPP / AD / Co-extrusion OPP / A / PO CPP / AD / K cellophane / ELPO OPP / AD / VM-PET / AD / PO PET / AD / VM-OPP / AD / PO PET / AD / VM-ONY / AD / PO PET / AD / AL / AD / PO stretched PO / AD / AL / AD / PO coextrusion OPP / AD / PET / AD / PO PO / AD / PET / AD / PO PET / AD / SiO-VM-PET / AD / PO PET / AD / SiO -VM-ONY / AD / PO PET / AD / SiO-VM-OPP / AD / PO paper / AD / AL / AD / PO OPP / AD / cellophane / AD / AL / AD / CPP glassine paper / AD / AL / AD / PO OPP / AD / CPP paper / AD / AL / ionomer

The meanings of the abbreviations are as follows. AC: Anchor coat layer AD: Adhesive layer PO: Polyolefin resin layer EL: Extrusion lamination method KOP: Vinylidene chloride coated biaxially oriented polypropylene resin film Layer PET: Polyethylene terephthalate resin film layer CPP: Unstretched polypropylene resin film layer K: Vinylidene chloride coat NO-NY: Unstretched nylon resin film layer O-NY: Stretched Nylon resin film layer EVOH ... Ethylene vinyl alcohol resin film layer VM ... Vacuum deposition AL ... Aluminum foil SiOVM ... Silicon oxide vacuum deposition layer

Next, representative examples of coloring substances for each color will be described. Black; carbon black, iron black (iron tetroxide), graphite (graphite), mineral black, aniline black, etc. White; titanium oxide, calcium carbonate, mica, zinc white, clay, barium sulfate, calcium sulfate, antimony white,
Lead white, lithopone, magnesium silicate, etc. Yellow; titanium yellow, yellow iron oxide, chrome yellow,
Zinc yellow, cadmium yellow, ocher, pigment yellow L, hansa yellow 3G, etc. Red; red, red, cadmium red, bon red 2B,
Carmine 6B, pyrazolone red, lake red C, lead red, permanent red 4R, etc. Blue; cobalt blue, ultramarine, navy blue, phthalocyanine blue, indanthrene blue, indigo, cyanine blue, etc. Green; chrome oxide green, titanium green, zinc green , Emerald green, cobalt green,
Pigment Green, Phthalocyanine Green, Cyanine Green and the like. It is preferable in that it has good photographic properties and has a synergistic effect of preventing oxidation.
When color printing is performed, the surface of the laminated film is preferably colored white, gray, yellow, or silver from the viewpoints of appearance, luminosity of printing, and the like.

The surfactant for ensuring the antistatic property, which is preferably contained in the laminated film used in the collective package of photographic light-sensitive materials of the present invention, is particularly a fluorine-based surfactant in that it does not adversely affect the photographic properties. Is preferable, but typical examples of the usable examples are shown below. Content is 0.01 to 10
% By weight, preferably 0.02 to 8% by weight, particularly preferably 0.05 to 5% by weight. [Fluorine] Nonionic, anionic, cationic and zwitterionic surfactants having a perfluorocarbon chain having 4 to 18 carbon atoms. (Example) C ₁₀ F ₂₁ SO ₄ N (CH ₃ ) CH ₂ COOK or C
₁₀ F ₂₁ SO ₂ N (CH ₃ ) CH ₂ COOK [nonionic] (= nonionic) (1) Alkylamine derivative; alkylamide type (laurylamine), N, N-bis (2-hydroxyethyl cocoa) Min), tertiary amine (2) fatty acid amide derivative; hydroxystearic acid amide, oxalic acid-N, N'-distearylamide butyl ester, polyoxyethylene alkylamide (3) ether type polyoxyethylene alkyl ether, poly Oxyethylene alkyl phenyl ether, special nonionic type (4) Polyhydric alcohol ester type glycerin fatty acid ester; mono-, di-, or trigulariseride such as stearic acid or hydroxystearic acid, sorbitan fatty acid ester, 1-hydroxyethyl-2 -Dodecylglyoxazoline

[Anionic] (1) Sulfonic acids; alkyl sulfonate, alkylbenzene sulfonate, alkyl sulfate (2) Phosphate ester type; alkyl phosphate

[Cation] (1) Amide-type cation (2) Quaternary ammonium salt; quaternary ammonium chloride, quaternary ammonium sulfate, quaternary ammonium nitrate, stearamidopropyl-dimethyl-β
-Hydroxyethyl ammonium nitratc

[Amphoteric ion system] (1) Alkyl petaine type (2) Imidazoline type (3) Alkyl imidazoline type (4) Metal salt type

Also, 776 to 776 of the Plastic Data Handbook (published by the KK Industrial Research Association on April 5, 1984)
From the various antistatic agents and the like disclosed on page 778, it is possible to select and use a kind and an addition amount which do not adversely affect the photographic properties of the photographic light-sensitive material.

Among the above surfactants, nonionic surfactants are particularly preferred because they have a small adverse effect on photographic properties and human body and have a large effect of preventing stitch marks.

Representative examples of the deodorant and the fragrance which are preferably contained in the laminated film used for the photographic light-sensitive material assembly package of the present invention are described below.

Examples of the deodorant include an organic carboxylic acid, a mixture of an organic carboxylic acid and a zinc compound, and a mixture of an organic carboxylic acid, a zinc compound and an aluminum compound.

Examples of the organic carboxylic acids include aliphatic polycarboxylic acids, aromatic polycarboxylic acids, and acidic polyester compounds having a carboxyl group at the end of the reaction product of these aliphatic or aromatic polycarboxylic acids with a polyhydric alcohol compound. There is.

The aliphatic polycarboxylic acids include oxalic acid, malonic acid, succinic acid, adipic acid, fumaric acid, methyl fumaric acid, maleic acid, methyl maleic acid, itaconic acid, acetylenic acid, malic acid, methyl malic acid, citric acid There are di- or tricarboxylic acids such as acid, isocitric acid, mesaconic acid and citraconic acid, and salts thereof, and particularly preferred are citric acid, fumaric acid and salts thereof.

Examples of the aromatic polycarboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, benzenehexatricarboxylic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid and azobenzenetetracarboxylic acid And benzenetricarboxylic acid and trimellitic acid are particularly preferred.

Examples of the acidic polyester compound having a terminal carboxyl group include polyester having a terminal carboxyl group obtained by reacting a polycarboxylic acid such as phthalic acid with a polyhydric alcohol such as ethylene glycol or diethylene glycol, or an acidic cellulose derivative modified with a polycarboxylic acid. Etc. Zinc compounds used in combination with the organic carboxylic acid include zinc oxide, zinc chloride, zinc sulfate, zinc phosphate,
There are inorganic zinc salts of zinc carbonates and organic zinc such as zinc citrate and zinc fumarate.

The fragrance includes natural flavor components such as lilac flower oil, jasmine, abies oil, cinnamon oil, lavender oil, lemon oil, geraniol, eugenol, n-
Octyl alcohol, carbitol, cis-chasmon, lemon terpene, menthone, methyl salicylate, methylphenylcarbinol, triethyl citrate,
Synthetic aromatic components such as benzyl benzoate, citral, d-linemon, geraniol, ethyl cinnamate, octanol, benzyl benzoate, alkylene glycol, benzyl salicylate, linalool, vanillin, coumarin, methyl naphthyl ketone, and rosephenone are microcapsule particles. It is used after being encapsulated in dextrin, cyclodextrin, maltosyl cyclodextrin, cyclodextrin, zeolite, starch, talc and the like.

The hydrotalcite compounds preferably contained in the laminated film used in the photographic light-sensitive material assembly package of the present invention are described below. Neutralizes catalyst residues, detoxifies substances that adversely affect photographic properties by absorbing halogen compounds such as hydrochloric acid, prevents resin burning failure, prevents blocking, and prevents the occurrence of bumps For example, at least 0.001 to 5.0% by weight, preferably 0.005 to 4.0% by weight of a hydrosite compound represented by the following and / or a fatty acid metal salt.
%, Particularly preferably 0.001 to 3.0% by weight, most preferably 0.02 to 2.0% by weight. If it is less than 0.001% by weight, the effect of addition is not exhibited, and only the kneading cost is increased. Not only does it cost money.

The hydrotalcite compound has the general formula
But M_XR_Y(OH)_{2x + 3y-2z}(A)_z・ AH_TwoO ｛M is Mg, Ca or Zn, R is Al or Cr or F
e, A is CO_ThreeOr HPO _Four, X, y, z, a are positive numbers.
Is a double salt represented by

As a typical example, Mg ₆ Al
_{2 (OH) 16 CO 3 ·} 4H 2 O, Mg 8 Al 2 (OH)
_{20 CO 3 · 5H 2 O,} Mg 5 Al 2 (OH) 14 CO 3 ·
_{4H 2 O, Mg 10 Al 2} (OH) 22 (CO 3) 2 · 4H
_{2 O, Mg 6 Al 2 (} OH) 16 HPO 4 · 4H 2 O, C
a ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Zn ₆ Al _{2
(OH) 16 CO 3 · 4H} 2 O, Mg 4.5 Al 2 (OH)
There is a ₁₃ · 3.5H ₂ O and the like.

Alternatively, when the general formula is M _(1-X) . _{Al x · (OH) 2 X} x / n · mH 2 O { However Shikichu, M is an alkaline earth metal and Zn. X represents an n-valent anion. And x and
m and n satisfy the following conditions. 0 <x <0. 0 ≦ m ≦ 2 A hydrotalcite compound having a refractive index (measured by Larsen's oil immersion method) in the range of 1.40 to 1.55 represented by an integer of n = 1 to 4. Examples of the n-valent anion represented by X in the above formula include Cl ⁻ , Br ⁻ , I ⁻ , NO
₃ ⁻ , ClO ₄ ⁻ , SO ₄ ²⁻ , CO ₃ ²⁻ , SiO ₃ ²⁻ ,
HPO ₄ ²⁻ , HBO ₃ ²⁻ , PO ₄ ³⁻ , Fe (C
^{_{N) 6 3-, Fe (CN}} ) 4 4-, CH 3 COC -, C 6 H
₄ (OH) COO ^- is.

Preferred specific examples are shown below. Mg _0.7 Al _0.3 (OH) ₂ (CO ₃ ) _0.15・ 0.54H ₂
O Mg _0.67 Al _0.33 (OH) ₂ (CO ₃ ) _0.165・ 0.54H
_{2 O Mg 0.67 Al 0.33 (OH} ) 2 (CO 3) 0.155 · 0.54H
₂ O Mg _0.6 Al _0.4 (OH) ₂ (CO ₃ ) _0.2・ 0.54H ₂
O Mg _0.75 Al _0.25 (OH) ₂ (CO ₃ ) _0.125・ 0.54
H ₂ O Mg _0.83 Al _0.17 (OH) ₂ (CO ₃ ) _0.085・ 0.54
H ₂ O etc. These hydrotalcite compounds may be natural products or synthetic products. These hydrotalcite compounds are mainly composed of magnesium, aluminum, etc., and have an adverse effect on the photographic properties of photographic light-sensitive materials and chlorine ions, which are considered to be a cause of rusting of metals used in molding machines. Is excellent in the ability to adsorb and detoxify halide ions. Further, it is presumed that it stabilizes the adsorption of substances that adversely affect photographic properties, such as monomers in thermoplastic resins and volatile substances in various additives. As a specific method for synthesizing the hydrotalcite compounds, known methods disclosed in JP-B-46-2280 and JP-B-50-30039 can be used.

In the present invention, the above-mentioned hydrotalcite compounds are particularly preferable, and they can be used without being limited by their crystal structures and crystal particle diameters. Natural products of hydrotalcite compounds include hydrotalcite, stichtite, pyroaulite and the like. These hydrotalcite compounds may be used alone or in combination of two or more. In particular, the use in combination with various antioxidants and various fatty acid metal salts described below does not deteriorate photographic properties,
It is preferable from the viewpoint of improving the dispersibility of the light-shielding substance and the hydrotalcite compound. In order to particularly improve film formability, physical properties, etc., the average secondary particle diameter is 20 μm or less, preferably 10 μm or less, particularly preferably 5 μm or less, and BET.
The specific surface area is 50 m ² / g or less, preferably 40 m ² / g, particularly 30 m ² / g or less.

In the present invention, it is preferable to use the hydrotalcite compound after treating it with a surface coating substance, since this improves the dispersibility. By coating the surface, dispersibility or affinity for resin is further improved, suitability for injection molding,
Physical strength and the like are also improved.

As examples of such a surface coating substance, the above-mentioned surface coating substances (1) to (20) of a light-shielding substance can be used. Potassium phosphate, sodium oleate, potassium oleate, calcium oleate, magnesium stearate, sodium stearate, zinc stearate, potassium stearate, sodium palmitate, potassium palmitate, sodium caprate, potassium caprate, sodium myristate Metal salts of higher fatty acids such as sodium, potassium myristate, sodium linoleate, potassium linoleate; higher fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, capric acid, myristic acid, linoleic acid; dodecyl Calcium benzenesulfonate, dode Metal salts of organic sulfonic acids such as sodium silbenzenesulfonate; isopropyltriimestearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, vinyltriethoxysilane, gamma methacryloxypropyltrimethoxysilane Coupling agents such as gamma glycidoxypropyltrimethoxysilane,
Examples include various lubricants such as higher fatty acid amides, higher fatty acid esters, silicones, and waxes.

The surface coating with these surface coating substances can be performed, for example, by adding an aqueous solution of an alkali metal salt of a higher fatty acid to a suspension of the hydrotalcite compound in warm water with stirring. It can be carried out by dropping a solution of a higher fatty acid or a diluting solution of a coupling agent while stirring the talcite compound powder with a mixer such as a Henschel mixer. The amount of these surface coating substances can be appropriately selected and changed, but based on 100 parts by weight of the hydrotalcite compound, about 0.01 to 50 parts by weight, preferably 0.05 to 35 parts by weight, particularly preferably 0.1 to 50 parts by weight.
20 parts by weight, most preferably about 0.5 to 10 parts by weight is suitable.

Further, a small amount of other impurities such as metal oxides may be contained as long as the gist of the present invention is not impaired. In order to further improve the dispersion of hydrotalcite compounds, for example, higher fatty acids, fatty acid amide-based lubricants, sorbitan fatty acid esters such as silicone oil and sorbitan monostearate, and glycerin fatty acid esters such as glycerin monostearate. One or more dispersants may be added to the resin composition in a total amount of 0.01 to 10% by weight, preferably 0.05 to 8% by weight, particularly preferably 0.08 to 5% by weight, and most preferably 0.1 to 3% by weight. . By using in combination with hydrotalcite compounds, the deterioration of photographic properties, the stability of injection molding, the anticorrosion (also called rust prevention) effect of injection molding machines and molds are improved, and the coloring of laminated films and resin deterioration In addition to the above, the effect of improving transparency, preventing a decrease in physical strength, and preventing the occurrence of spots and coloring failure due to resin burning is synergistically improved. When used in combination with one or more stabilizers selected from the group consisting of phenolic antioxidants, phosphorus (phosphite) antioxidants and fatty acid metal salts, the photographic properties of the photographic material are hardly deteriorated, and the molding machine It is particularly preferable because the corrosion and rust prevention and oxidation prevention effects of the metal mold and the die are increased.

In this case, in order not to adversely affect the photographic performance of the photographic material, (1) a phenolic antioxidant is added in an amount of 0.0005 to 0.5% by weight to the laminated film used for the collective packaging of the photographic material. Preferably 0.001 to 0.4% by weight, particularly preferably 0.002 to
Add 0.3% by weight. (2) Phosphorus antioxidant 0.0005 to 0.5% by weight, preferably
0.001 to 0.4% by weight, particularly preferably 0.002 to 0.1% by weight. (3) Hydrotalcite compounds and fatty acid metal salts (metal soaps), or any one or more of them
01 to 5% by weight, preferably 0.005 to 4% by weight, particularly preferably 0.01 to 3% by weight. And the total content of (1) + (2) + (3) is 0.0015 to 6% by weight, preferably 0.002 to 5% by weight, and particularly preferably 0.0
03 to 4% by weight, most preferably 0.005 to 3% by weight. In any case, these additives do not deteriorate the photographic performance when added in the minimum amount that can prevent resin deterioration,
This is preferable from the viewpoint of preventing bleed-out and suppressing cost increase.

Further, it is preferable to use together with the hydrotalcite compound, and not only exhibits the same excellent effect as the hydrotalcite compound, but also exhibits the effect as the dispersibility of the lubricant and the light-shielding substance. The following describes the fatty acid metal salt (also referred to as metal soap).

Representative examples of fatty acid metal salts include lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid,
Higher fatty acids such as phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, erucic acid and Li, Na, Mg, Ca, Sr,
Compounds with metals such as Ba, Zn, Cd, Al, Sn, Pb, and Cd are preferred, and preferred are magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate,
Zinc oleate, magnesium oleate and the like.

Further, one or more of an inorganic nucleating agent and an organic nucleating agent can be added to the laminated film used for the photographic light-sensitive material assembly package of the present invention. By adding one or more of an inorganic nucleating agent and an organic nucleating agent, surface hardness, rigidity, impact strength, abrasion resistance and the like can be improved. In addition, when added to a polyolefin resin of a crystalline resin, particularly a homopolyethylene resin, an ethylene-α-olefin copolymer resin, and a propylene-α-olefin copolymer resin, the transparency and the moldability are improved in addition to the above properties. it can.

The total content of one or more of the inorganic nucleating agent and the organic nucleating agent is preferably 0.001 to 10% by weight, more preferably 0.005 to 8% by weight, and 0.01 to 10% by weight. 5
% Is most preferred. Total content is 0.001% by weight
If it is less than the above, there is no effect of inclusion and only the kneading cost increases. On the other hand, when the total content exceeds 10% by weight, there is no effect of increasing the amount, and only the cost increases. Further, in the case of an organic nucleating agent, smoke is increased during injection molding, and bleeds out to the surface of the injection-molded product over time to deteriorate the appearance. Further, a problem arises that white powder is formed and adheres to the photosensitive layer of the photographic light-sensitive material to cause development inhibition.

Examples of the organic nucleating agent that can be used in the present invention include:
Carboxylic acids, dicarboxylic acids, salts and anhydrides thereof, salts and esters of aromatic sulfonic acids, aromatic phosphinic acids, aromatic phosphonic acids, aromatic carboxylic acids, other aluminum salts, metal salts of aromatic phosphates, carbon Examples include alkyl alcohols of Formulas 8 to 30, condensates of polyhydric alcohols and aldehydes, and alkylamines.
Aluminum butyl benzoate, 1,2,3,4-dibenzylidene sorbitol, disubstituted benzylidene sorbitol compound represented by the formula ( _{2) wherein} R ₁ and R ₂ are alkyl, alkoxy or halogen having 1 to 8 carbon atoms. Yes, m
And n are each 0 to 3 and m + n ≧ 1. ｝, A metal salt of stearyl lactic acid such as calcium or magnesium, or a compound represented by Chemical formula 3 such as N- (2-hydroxyethyl) -stearylamine ｛wherein R ₃ is an alkyl group having 8 to 30 carbon atoms. , K and l are each 0 to
10 and k + 1 ≧ 1.金属, metal salts such as lithium salt, sodium salt, potassium salt, calcium salt and magnesium salt of 1,2-hydroxystearic acid, alkyl alcohols such as stearyl alcohol and lauryl alcohol, sodium benzoate, benzoic acid, sebacic acid and the like. is there.

Representative examples of particularly preferred sorbitol compounds among the organic nucleating agents are shown below. di- (o-methylbenzylidene) sorbitol o-methylbenzylidene-p-methylbenzylidenesorbitol di- (o-methylbenzylidene) sorbitol m-methylbenzylidene-o-methylbenzylidenesorbitol di- (o-methylbenzylidene) sorbitolh m-methylbenzylidene-p-methylbenzylidenesorbitol 1.3-heptanylidenesorbitol 1,3,2,4-diheptanylidenesorbitol 1,3,2,4-di (3-nony1-3-pentenylidene) sorbito
l 1,3-cyclohexanecarbylidenesorbitol 1,3,2,4-dicyclohexanecarbylidenesorbitol 1,3,2,4-di (p-methylcyclohexanecarbylidene) s
orbitolAromatic hybrocarbon groups or derivatives
there 1,3-benzylidenesorbitol 1,3,2,4-dibenzylidene-D-sorbitol 1,3,2,4-di (m-methylbenzylidene) sorbitol 1,3,2,4-di (p-methylbenzylidene) sorbitol 1・ 3,2,4-di (p-hexylbenzylidene) sorbitol 1,3,2,4-di (l-naphthalenecarbylidene) sorbito
l 1,3,2,4-di (phenylacetylidene) sorbitol 1,3,2,4-di (methylbenzylidene) sorbitol 1,3,2,4-di (ethylbenzylidene) sorbitol 1,3,2,4-di ( propylbenzyledene) sorbitol 1,3,2,4-di (methoxybenzylidene) sorbitol 1,3,2,4-di (ethoxybenzylidene) sorbitol 1,3,2,4-di (P-methylbenzylidene) sorbitol 1,3,2 ・4-di (P-chlorbenzylidene) sorbitol 1,3,2,4-di (P-methoxybenzylidene) sorbitol 1,3,2,4-di (alkilbenzylidene) sorbitol 1,3,2,4-di (methybenzylidene) sorbitol aluminumbenzoate, etc.

Among the above-mentioned organic nucleating agents, the dibenzylidene sorbitol compound, which is particularly preferable in the present invention, is a polyolefin resin, for example, a polypropylene resin such as a homopolypropylene resin or a propylene / α-olefin copolymer (block type or random type) resin. And polyolefin resins such as low-density homopolyethylene resin, high-density homopolyethylene resin, linear polyethylene (ethylene / α-olefin copolymer) resin, and ethylene / propylene copolymer resin. Particularly, a crystalline polyolefin resin having a high crystallinity is preferable, and the crystallinity is 50% or more, preferably 70% or more, particularly preferably 80% or more, since the effect of adding the organic nucleating agent is effectively exhibited. Most preferably, it is a 90% or more polyolefin resin.
However, aldehydes are generated by thermal decomposition, which adversely affects the photographic properties of photographic light-sensitive materials. Therefore, unless the above-mentioned hydrotalcite is added to prevent thermal decomposition, practical application of L-LDPE resin is difficult. .

The molecular weight distribution (number-average molecular weight / number-average molecular weight) of these polyolefin-based resins is from 1.1 to 20, preferably from 1.3, in terms of balance between securing physical strength and ensuring moldability.
-15, particularly preferably 1.5-12, most preferably 1.8-10. It has now been found that the effect of adding the organic nucleating agent is exerted as the molecular weight distribution decreases. Therefore, when an organic nucleating agent is contained, the molecular weight distribution is 1.1 to 1
0, preferably 1.3-8, particularly preferably 1.5-6, most preferably 1.8-5. Where the molecular weight distribution is GP
It is determined from the measured molecular weight represented by weight average molecular weight / number average molecular weight by Method C. When the molecular weight distribution is less than 1.1, the physical strength is very good, and the dimensional accuracy is excellent in an injection molded product, but the injection moldability is deteriorated and the polymerization is difficult and expensive. When the molecular weight distribution exceeds 20, the reverse is true, and any of them is difficult to put into practical use.

In the polyolefin resin composition of the present invention,
By including the above-mentioned di-substituted benzylidene sorbitol compound, excellent photos such as physical strength, surface strength, surface hardness, rigidity, bleed-out resistance, odorlessness, transparency, photographic properties, moldability, abrasion resistance, etc. A laminated film for photosensitive material collective packaging can be provided.

The amount of free sulfur (JISK) in the moisture-proof case (P case) in which the photographic film described above is sealed and packaged
6350) is 50 ppm or less, preferably 30 ppm or less.
The amount of free formaldehyde (value according to the method for quantitative determination of free formaldehyde described in Polymer Analysis Handbook, KK Asakura Shoten, published March 1, 1986, page 375) is 10 ppm or less, particularly preferably 10 ppm or less.
If the raw materials used are not carefully selected so as to be 0 ppm or less, preferably 50 ppm or less, particularly preferably 25 ppm or less, photographic properties deteriorate.

The light-sensitive material packaged by the light-sensitive material assembly package of the present invention is not particularly limited. Examples thereof include a silver halide photographic light-sensitive material, a diffusion transfer photographic light-sensitive material, a non-silver halide photographic light-sensitive material, and a diazo photographic light-sensitive material. Examples of the material include photosensitive materials, photosensitive resins, light fixing type heat sensitive materials, heat developing type photosensitive materials, photosensitive heat sensitive materials, and photosensitive materials whose quality is deteriorated by light or moisture, such as a developing solution, a fixing solution, and a dye.

In the present invention, an antioxidant may be added in order to prevent thermal deterioration of the resin, lubricant and the like and to prevent adverse effects on the photographic properties of the photographic material. Representative examples of the antioxidant that can be used in the present invention are shown below. (A) phenolic antioxidant (t is an abbreviation for tert); vitamin E (tocopherol), 6-t-butyl-3-methylphenyl derivative, 2,6-di-t-butyl-P-cresol, 2,6-di-t-butyl-phenol, 2,6-di-t-butyl-α-dimethylamino-
P-cresol, 2,6-di-t-butyl-P-ethylphenol, 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, butylated hydroxyanisole, alkylated bisphenol, styrenated phenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, n-octadecyl -3- (3'-5'-di-t
-Butyl-4'-hydroxyphenyl) propinate,
2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-
t-butylphenyl), 4.4'-butylidenebis (3-methyl-6-t-butylphenol), 4.4 '
-Thiobis (3-methyl-6-t-butylphenol), stearyl-β (3.5-di-4-butyl-4-)
(Hydroxyphenyl) propionate, 1,1.3-tris (2-methyl-4hydroxy-5-tert-butylphenyl) butane, 1,3.5 trimethyl-2,4.6-tris (3.5-di- t-butyl-4hydroxybenzyl) benzene, tetrakis [methylene-3 (3 ′ · 5 ′)
-Di-t-butyl-4'-hydroxyphenyl) propionate] methane and the like

(B) Phosphite antioxidants; alkylated allyl phosphite, tris (mono and / or dinonylphenyl) phosphite, cyclic neopentanetetraylbis (2.6-di-t-butyl-) 4-methylphenyl) phosphite, diphenylisodecylphosphite, tris (nonylphenyl) phosphite sodium phosphite, tris (nonylphenyl) phosphite,
2,2-methylenebis (4.6-di-tert-butylphenyl) octyl phosphite, tris (2.6-di-tert-butyl)
Butylphenyl) phosphite, triphenyl phosphite, etc.

Representative examples of the most preferred hindered phenolic antioxidants for the present invention are shown below. 1,3,5-trimethyl 2,4,6-tris (3,5-di-tert-
Butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3'.5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, otatadecyl-3,5-di-tert-butyl-4
-Hydroxy-hydrocinnamate, 2,2 ′, 2′-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, 1,3,5-tris (4-tert. Butyl-
[3-hydroxy-2,61-di-methylbenzyl] isocyanurate, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphite, 4,4'-thiobis- (6- tert-butyl-o
Cresol), 2,2'-thiobis- (6-tert)
-Butyl-4-methyl-phenol), tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 4,4'-methylene- Bis (2,6-di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,6-di-tert
1-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, 2,
6-di-tert-14-n-butylphenol, 2,6
-Bis (2'-hydroxy-3'-tert-butyl-5'-methylbenzyl) -4-methylphenol,
4,4'-methylene-bis (6-tert-butyl-o
Cresol), 4,4'-butylidene-bis (6-1t)
tert-butyl-m-cresol), 3.9-bis@1
-1-dimethyl-21- [β- (3-t-butyl- 4-hydroxy-5-methylphenyl) propionyloxy]
Ethyl @ 2,4,8,10-tetraoxaspiro [5,
5] Undecane and the like. Among them, those having a melting point of 100 ° C. or higher, particularly 120 ° C. or higher are preferable.
Further, it is effective to use it in combination with a phosphorus antioxidant.

The chemical names, molecular weights, melting points, and trade names of typical commercially available antioxidants are shown below. (1) Phenolic antioxidant n-octadecyl-31 (3 ′, 5′-di-tert-
Butyl 4'-hydroxyphenyl-propionate (molecular weight 581, melting point 50-54 ° C, trade name; IRGANO
X1076 (Ciba Geigy), MARK AO-150
(Adeka Argus), SUMllLZER BP-17
6 (Sumitomo), TOMINOX SS (Yoshitomi). ), 2,
4-bis-[(n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5
-Triazine)] (molecular weight 589, melting point 91-96 ° C,
Trade name: IRGANOX565 (Ciba Geigy). ),
2,2'-methylene-bis- [6- (1-methylcyclohexyl) -p-cresol] (molecular weight: 421, melting point>
130 ° C, trade name: NONOX WSP (IC
I). ), 4,4'-thio-bis-((3-methyl-6
-Tert-butyl) phenol] (molecular weight: 358, melting point: 161 to 164 ° C, trade name: SANTONOX (Mo
nsanto), SUMIILZER WXR (Sumitomo), ANTAGE CRYSTAL (Kawaguchi). ),
2,2-thiodiethylene-bis- [3- (3,5-di-tert-butyl-4-hydroxy) phenyl] propionate (molecular weight 643, melting point> 63 ° C., trade name; IRGA
NOX1035 (Ciba Geigy). ), 2,2′-methylene-bis- (4-methyl-6-t-butylphenol) (molecular weight: 341; melting point> 120 ° C .; trade name: ANT)
AGE W-1400 (Kawaguchi), NOCLIZER NS
Sixteen (Ouchi Emerging). ), Calcium bis-[(ethyl-
3,5-di-tert-butyl) -4-hydroxybenzyl phosphate] (molecular weight 695, trade name; IRG)
ANOX1425WL (Ciba Geigy). ), 3,9,
Bis [1,11-dimethyl-2- {β- (31-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -1,2,4,8,10-tetraoxaspiro [5,5] undecane (Molecular weight 741, melting point 12
3-126 ° C, trade name: MARK AO-80 (ADEKA Argus), SUMLIZER GA-80 (Sumitomo). ), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane (molecular weight: 545, melting point: 185 to 188 ° C., trade name; TOPAN)
OL CA (ICI), MARK AO-30 (ADEKA Argus). ), Tris- (3,5-di-tert-butyl-4-hydroxydibenzyl) isocyanurate (molecular weight 784, melting point 218-223 ° C, trade name; MA)
RKAO-20 (Adeka Argus), IRGANOX
3114 (Ciba Geigy). ), 1.3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-14-hydroxydibenzyl) benzene (molecular weight 775, melting point 240 ° C., trade name; MARK AO-330 (ADEKA) Argus), IRGANOX1380 (Ciba Geigy).), Tris- (4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate (molecular weight 700, melting point 145-155 ° C, trade name; C)
YANOX 1790 (ACC). ), Tetrakis- [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxy-phenyl) propionate] methane (molecular weight 1,178, melting point 110-125 ° C, trade name;
IRGANOX1010 (Ciba Geigy), MARK
AO-60 (Adeka Argus), SUMLLZER
BP-1101 (Sumitomo), TOMINOX TT (Yoshitomi). )etc.

(2) Phosphorus antioxidant Tris (2.4-di-tert-butylphenyl) monophosphite (molecular weight: 647, melting point: 180 to I86 ° C., trade name: IRGAFOS168 (Ciba Geigy), MAR)
K2112 (Adeka Argus). ), Distearyl
Pentaerythritol diphosphite (molecular weight 78
3, melting point 152 ° C., trade name: weston 618 (BorgWarner), MARK PEP-18 (ADEKA Argus). ), Di (2,4-di-tert-butylphenyl) -pentaerythritol diphosphite (molecular weight 605, melting point 160-175 ° C, trade name; ULTRAN)
OX626 (BorgWarner), MARK PEP-12
4G (Adeka Argus). ), Bis- (2,6-di-)
tert-butyl-4-methylphenyl) pentaerythritol diphosphite (molecular weight: 633, melting point: ~ 28
7 ° C., trade name: MARKPEP-36 (ADEKA Argus). ), 9.10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (molecular weight 216,
Melting point 115 ° C, trade name: HCA (Sanko)) and the like. The molecular weight is preferably 200 or more, from the viewpoints that it does not adversely affect the photographic properties of the photographic light-sensitive material, generates less smoke and odor during film forming, has less bleed-out with time, and has little decrease in heat seal strength. Is more than 300,
More preferably 400 or more, particularly preferably 500 or more, and most preferably 600 or more antioxidants.

By improving the fluidity of the resin, the melt fracture can be improved.
Lubricants can be added to prevent the occurrence of blemishes and bumps, and as a result, the occurrence of abrasions on the photosensitive material, the occurrence of pressure fouling, and the like. The names of typical commercially available lubricants and manufacturers are described below.

(1) Fatty acid amide lubricant; [saturated fatty acid amide lubricant] Behenic acid amide lubricant; Diamid KN (Nippon Kasei) and the like. Stearamide amide-based lubricant; Armide HT (Lion fat), Alflo S110 (Nippon Oil & Fat), fatty acid amide S (Kao), Diamid 200 (Nippon Kasei), Diamid AP-11 (Nippon Kasei), Amide S
・ Amide T (Nitto Chemical), Neutron-2 (Nippon Saccharification) and the like.

[Hydroxystearic amide lubricant] Palmitic amide lubricant; Neutron S-118
(Nippon Saccharification), Amide P (Nitto Chemical) and the like. Lauric amide lubricants: Armide C (Lion Akzo), Diamid (Nippon Kasei) and the like.

[Unsaturated fatty acid amide lubricant] Erucamide amide lubricant: Alflow P-110 (Nippon Oil & Fats), Neutron-S (Nippon Saccharification), LUBROL
(ICI), Diamid L-200 (Nippon Kasei)
etc. Oleic amide lubricants; Armoslip CP (Lion Akzo), Neutron (Nippon Saccharification), Neutron E-118 (Nippon Saccharification), Amide O (Nitto Kagaku), Diamid O-200, Diamid G-20
0 (Nihon Kasei), Alflo E-10 (Nippon Oil & Fats), fatty acid amide O (Kao) and the like.

[Bis fatty acid amide lubricant] Methylene bisbehenic acid amide lubricant; Diamid NK bis (Nippon Kasei) and the like. Methylene bisstearic acid pumid-based lubricants such as Diamid 200 bis (Nippon Kasei), armowax (Lion Akzo), bisamite (Nitto Kagaku) and the like. Methylenebisoleic amide lubricant; Lubron O
(Nippon Kasei) and others. Ethylene bisstearic acid amide lubricant; Armoslip EBS (Lion Akzo) and the like. Hexamethylene bisstearic acid amide lubricant: Amide 65 (Kawasago Fine Chemical) and the like. Hexamethylenebisoleic amide lubricant: Amide 60 (Kawasago Fine Chemical) and the like.

(2) Hydrocarbon lubricant; liquid paraffin,
Natural paraffin, micro wax, synthetic paraffin,
Polyethylene wax (number average molecular weight is 10,000 or less, preferably 8,000 or less, particularly preferably 6,000 or less), polypropylene wax (number average molecular weight is 10.000 or less, preferably 8,000 or less, particularly 6 000 or less.), Chlorinated hydrocarbons, fluorocarbons and the like. (3) Fatty acid-based lubricants: higher fatty acids (preferably C ₁₂ or more; specifically, caproic acid, stearic acid, oleic acid, erucic acid, palmitic acid, etc.), oxy fatty acids and the like.

(4) Ester lubricants: lower alcohol alcohols of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, and the like. (5) alcohol-based lubricants: polyhydric alcohols, polyglycols, polycricerols and the like. (6) Metallic soap; higher fatty acids such as lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, erucic acid and L
i, Na, Mg, Ca, Sr, Ba, Zn, Cd, A
Examples thereof include compounds with metals such as 1, Sn, Pb, and Cd, and preferred are magnesium stearate, calcium stearate, zinc stearate, and magnesium oleate.

(7) Silicone-based lubricants: Various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Toray Silicone), especially various silicone oils, not only exhibit the effects of improving resin fluidity and lubricity, but also When used together with a light-shielding substance, the dispersibility of the light-shielding substance is improved, and the resin becomes cloudy when used together with a light-shielding substance.
As a result of increasing 3), unexpected effects such as improvement in coloring power and improvement in light-shielding properties are exhibited, which is preferable.

CAS code (camera automatic detection code),
Bar codes, CI marks, product names, instruction manuals, product identification marks, product identification colors, and other necessary characters and symbols for functions, or printing to enhance product value can be performed. Alternatively, when a shrink film, label or label stretched at least in the longitudinal direction on which these prints are applied is attached to the molded article of the present invention or heat-shrinkable and attached to form a photo-sensitive material assembly package, the package is opened linearly in the longitudinal direction. This is possible because it becomes possible. As the ink used for these printings, those having little or no harm to the photographic light-sensitive material are selected, and generally used offset printing inks, gravure printing inks or U inks are used.
It can be selected from V ink and the like.

Typical synthetic resins used for these inks are copolymer resins mainly composed of vinyl chloride, vinyl: amino resin, alkyd / vinyl resin, oil-free alkyd resin, vinyl chloride-based resin, Cotton, polyester resin, polyamide resin, urethane resin, polyacrylic resin, rosin-modified maleic acid resin, ethylene vinyl acetate copolymer resin, vinyl ether resin, urethane vinyl acetate copolymer resin, biurethane hydrochloride resin, modified alkyd resin, modified Phenol resin, high molecular polyester / amino resin, low molecular polyester / amino resin, alkali-soluble resin (rosin-modified maleic resin, styrene maleic resin, styrene acrylate resin, acrylate acrylate resin, methacrylate acrylate Acid resin), hydrosol Resin (styrene-maleic acid resins, styrene-acrylic acid resin, alpha one methyl styrene acrylate resins, acrylic ester acrylic resin, a methacrylic acid ester-acrylic acid resin), emulsion type resins (styrene resin, styrene-acrylic acid ester resin,
Acrylic ester copolymer resins, methacrylic ester copolymer resins), and resins having acrylic unsaturated groups are generally used as resins for VU inks.
Typical examples are polyester / acrylate resin, polyester / urethane resin / acrylate, epoxy resin / acrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, hexanediol diacrylate, neopentyl glycol diacrylate. , Triethylene glycol diacrylate, hydroxyethylene methacrylate and the like.

Further, a generally known coloring agent is used in combination with these inks. As the coloring agent used,
Various pigments and azo pigments described in JP-A-63-44653 and the like (azo lake; carmine 6B, red 2B, insoluble azo; monoazo yellow (PY-1,3)),
Disazoyello (PY-Is 12, 13, 14, 17, 8)
3), pyrazolo orange (PO-B-34), vulcan orange (PO-116), condensed azo type; chromobutaluiero (PY-93, 95), chromophthal red (PR
144, 166), polycyclic pigments (phthalocyanine-based pigments;
Copper phthalocyanine blue (PB-15, 15-1, 15
-3), copper phthalocyanine green (PG-7), cyoxazine type; dioxazine violet (PV-2
3), isoindolinone type; isoindolinone yellow (PY-109, 110), sulene type: perylene, perinone, flavanthrone, thioindigo, lake pigment (malachite green, rhodamine B, rhodamine G, Victoria blue B) or inorganic Pigment (oxide; titanium dioxide,
Bengala, sulfate; precipitated barium sulfate, carbonate; precipitated calcium carbonate, silicate; hydrous silicate, anhydrous silicate,
Metal powder; aluminum powder, bronze powder, zinc powder, other carbon black, graphite, ultramarine, navy blue) and the like.

These pigments may be added to the above-mentioned resin layer or the like as a light-shielding substance. In addition, oil-soluble dyes, dispersible dyes and the like are also used. In addition, various solvents, dispersants, wetting agents, disinfectants, leveling agents, thickeners, stabilizers, cross-linking agents,
Additives such as wax are used. Synthetic resins and colorants used as these ink compositions are applied to the surface of molded articles as paints to improve commercial value, improve abrasion resistance,
It is also preferable to use it for the purpose of improving light-shielding properties and improving photographic properties.

Various paints can be applied as a base coat or a top coat to improve the commercial value and make the printing of the printing ink beautiful and colorful. As the coating resin and pigment, those for the ink described above can be used, but UV coating, melamine alkyd coating, urethane coating, and melamine coating are particularly preferable. Topcoat is made of transparent lacquer paint, silicone paint, urethane paint, acrylic lacquer paint. 1 to 30 μm, preferably 0.3 to 20 μm, particularly preferably 0.5 to 10 μm
m.

The applicable photographic materials are shown below. (1) Silver halide photographic materials (printing film, color or black and white photographic paper, color or black and white negative film, printing master paper, DTR (diffusion transfer) photosensitive material,
Computer typesetting film and paper, color or black-and-white positive film, color reversal film, microfilm, movie film, self-developing photographic light-sensitive material, direct positive film and one-par film etc.)

(2) Heat-developable light-sensitive materials (heat-developable color light-sensitive materials, heat-developable black-and-white light-sensitive materials (for example, JP-B-43-492)
Nos. 1 and 43-4924, "Basics of Photographic Engineering", pp. 553 to 555 of "Silver Salt Photo Edition" (published by Corona Co., Ltd., 1879), and Research Tis Closure Magazine 197.
What is described in pages 9 to 15 of June, 1996 (RD-17029). Further, a transfer type heat-developable color photographic light-sensitive material described in JP-A-59-11431, JP-A-60-2950, JP-A-61-52343 and U.S. Pat. ))

In order that these photographic materials can maintain good photographic properties for a long period of time (6 months or more), the photographic materials have a water vapor transmission rate (measured under the condition B of JIS Z 0208).
Is 10 g / m ² · 24 hours or less, preferably 5 g / m ²
m ² · 24 hours or less, particularly preferably 2 g / m ² · 24
Less than time, oxygen permeability is 50cc / m ² · 24 hours · 1
Atmospheric pressure / 20 ° C or less, preferably 35 cc / m ² · 24 hours · 1 atm / 20 ° C or less, particularly preferably 20 cc / m
It is preferred to as a sealed package body comprising a ^2-24h · l pressure-20 ° C. or less.

The photographic light-sensitive material packaging material of the present invention uses the above-described photographic light-sensitive material, and the photographic light-sensitive material has a moisture permeability (Jls).
Z 0208, condition B) is 10 g / m ² · 24 hours or less, and oxygen permeability (mocon same measurement method) is 50 cc / m.
Is configured as characterized by being a sealed package with ² 24h · l pressure-20 ° C. or less.

When the water vapor transmission rate exceeds 10 g / m ² · 24 hours, the photographic properties of the photographic material containing a large number of sensitizing dyes and various additives which degrade from water are kept in a good state for a long time (6 months or more). I can't keep it. Further, since a gelatin layer which easily blocks when moisture is absorbed is present at least on one of the front and back surfaces of the support, blocking is likely to occur, and practical use is difficult.

The oxygen permeability is 50 cc / m ² · 24 hours.
When the pressure exceeds 1 atm / 20 ° C., sensitizing dyes degraded by oxygen, couplers and other additives in the emulsion coating layer of a photographic light-sensitive material which is easily oxidized are deteriorated and photographic properties are deteriorated, so that practical use is difficult. In particular, it is difficult to practically use a color photographic light-sensitive material (a negative film, a positive film, a photographic paper, a reversal film, an instant film, etc.) which requires a color balance.

The molded article for a photographic material of the package of the photographic material may contain, adhere to or coat the above-mentioned deodorant, fragrance, hygroscopic agent or oxygen scavenger.

Instead of the moisture-proof bag, it can be packaged in an easy-opening cosmetic box. As shown in FIG. 7, the easy-to-open cosmetic box 38 has a perforation 39 on the side surface, and can be easily opened by pressing the central portion. As shown in FIG. 8, the easily-openable decorative box 40 has a perforation 41 at the center formed in an arc. In addition, as shown in FIG.
Like the packaging bag 28, it is a type that can be hung, and the tongue 4
3 has a hole 43a for suspension.

The paperboard for a decorative box used in the present invention will be described. As for the material used, the surface layer on the photographic light-sensitive material side is made of conifers (cedar, Karamatsu, Akamatsu, Kuromatsu, Ezomatsu, Todomatsu,
Fiber diameter of fir, cypress, spruce, hemlock etc. is about 30-45
μm, fiber length of about 2.5 to 4.0 mm) and broadleaf trees (hippo, maple, beech, alder, elm, drill, chestnut, etc.) with a fiber diameter of about 20 to 40 μm and a fiber length of about 0.5 to 2. 0m
m) and wood fibers such as eucalyptus and virgin wood fibers such as non-wood fibers such as kenaf, bagasse, jute, bamboo, and esparto grass. The back layer and the intermediate layer on the photographic material side are preferably made of waste paper or waste paper and virgin. May be used in combination. Further, non-wood fibers such as kenaf, bagasse, jute, bamboo, esparto grass, mulberry, mitsumata, seaweed and straw, and fast-growing wood fibers such as eucalyptus may be used. Still further, synthetic pulp or synthetic chemical fiber may be mixed and used.

These wood fibers and non-wood (vegetable) fibers and their components are mainly composed of cellulose, hemicellulose and lignin, and also contain a small amount of extracted components and ash. Typical examples of paperboards for paper containers used for decorative boxes are coated manila cardboard and uncoated manila cardboard as white paperboard, coated white cardboard and uncoated white cardboard, yellow paperboard, and chipboard as back white. There are chip cardboard, general chip roll paper, and kraft cardboard as colored paperboard.

[0137] Manila balls usually have a rice weighing of 200-3.
Was 200 g / m ² approximately, the surface layer bleached chemical pulp, the intermediate backing layer made by blending ground wood pulp, chemical pulp, waste paper and the like. The white ball is weighed 200-400g /
m is up to ^2, exposed to the surface chemical pulps, the middle backing layer made by blending waste paper, other pulp. On waste paper,
There are newspapers, magazines, corrugated cardboard waste and cement bags collected, as well as high quality waste paper generated in printing shops and factories. The waste paper is returned to fibrous pulp by high-speed stirring with water in a disintegrator called pulper, and then used.

A typical layer constitution of the uncoated white cardboard is a surface layer (Nishi-Kraft pulp 100% (whiteness 90%)) /
Lower surface layer (newspaper waste paper, deinked / bleached pulp 100% (whiteness 70-80%)) / middle layer (newspaper waste pulp 100%)
/ Intermediate layer (100% newspaper waste pulp) / Intermediate layer (100% newspaper waste pulp) / Back layer (100% newspaper waste pulp)
It is.

The typical layer constitution of coated white cardboard is as follows: coating layer / surface layer (Nishi-Kraft pulp 100% (whiteness 90
%)) / Lower layer (newspaper, 100% deinked / bleached pulp)
(Whiteness 70-80%)) / intermediate layer (newspaper waste pulp 1)
00%) / intermediate layer (newspaper pulp 100%) / intermediate layer (newspaper pulp 100%) / back layer (newspaper pulp 1)
00%).

The yellow paperboard is a paperboard made using straw pulp. The colored paperboard is a paperboard made by using a raw material colored in the surface layer, and includes double-sided kraft balls, single-sided kraft balls, tea balls, rat balls and the like.

[0141] Note that the paperboard is not suitable for productivity and strength.
It is preferred that the paper be a substrate of more than one layer. As a method for producing a paperboard, a combination method in which the surface layer is formed by a long or short netting paper machine and the other layers are formed by a circular netting machine is preferable for the following reasons. Long net or short net paper machines have no difference in the vertical and horizontal properties of paper compared to circular net paper machines, and have higher productivity.
Ideal for making the surface layer of paperboard. A round paper machine has a greater difference in vertical and horizontal properties and a lower productivity than a fourdrinier or short net paper machine, but has the advantage that the number of layers can be increased and the raw material can be changed for each layer. It is most suitable for making a plurality of intermediate layers and back layers.

[0142] Since the pulp fiber alone cannot provide sufficient surface smoothness and printability of paperboard, an opaque paint (clay, colorant, starch, casein, etc.) having a high ink receptivity was used as a binder on the surface layer. Paint) to form a coating layer and cover the unevenness of the surface to form a uniform and smooth surface, so that the appearance of the paperboard can be improved, modified, printable, printable, and printed. Workability can be improved. Also,
The same effect can be obtained by laminating high quality paper, kraft paper, glassine paper or the like on the surface.

The use of the following chemicals can improve various drawbacks of pulp and waste paper, which are the main raw materials of paperboard. If only pulp is used, the ink absorbs too well and is sensitive to atmospheric conditions, so a sizing agent (pine resin size, petroleum resin size, wax size, etc.) is added to fix the ink to the fibers. Aluminum sulfate is added to allow for

The addition of a paper strength enhancer can increase the burst strength and tensile strength. Paper strength enhancers include natural products and synthetic products. The former includes starch (corn starch, potatoes, etc.), vegetable gums (coar gum, locust bean), higher fatty acids, water-soluble cellulose, modified starch and the like. The latter includes polyacrylamide, copolymer latex, various polyvinyl alcohols, alkyl ketene dimers, styrene / acrylic resins, urea resins, and the like. If the sizing agent alone is not sufficient, a waterproofing agent is added internally or applied to the surface. The mildest water resistance is a wax emulsion surface coat (water repellent). Furthermore,
In order to prevent the inter-fiber strength from weakening when immersed in water, urea resin, miramine resin, polyacrylamide resin, or the like is used because on-machine processing in the papermaking process is possible and waste paper can be recovered.

In addition, in the pulping step, an antiadhesive agent for scale, a penetration enhancer for cooking liquor, an antifoaming agent, and the like are used as chemicals for improving efficiency and yield. In the papermaking process, dewatering improvers (polyethyleneimine) and slime inhibitors (chlorine, sulfur, tin) are used, and the basic unit of papermaking has been improved by extending the life of papermaking wires and cleaning agents for blankets. .

When a coating agent is added, printability is improved, abrasion resistance is improved, warpage is prevented, whiteness by fuel coating,
The printability can be improved and the surface can be colored. To improve printability and abrasion resistance, starch, PVA, CM
C, a wax-based chemical is used. Examples of the coating agent include a coating material for forming the above-mentioned coating layer. The raw materials, types and characteristics of coating agents for paints are shown below.

[0147] 1. 1. Dyes (mainly for color tone; colored dyes and yellow light dyes) Pigments (mainly for the purpose of improving ink acceptability, whiteness, opacity, smoothness, glossiness, etc.) (1) Clay (kaolin) (kaolinite, hydrohalosite, sericite, pyrite clay) [Features] Plays a major role in improving printability such as gloss, smoothness, ink acceptability, whiteness, and opacity of paper. Main component of pigment. (2) Calcium carbonate (precipitable calcium carbonate, pulverizable calcium carbonate) [Features] Improvement in whiteness, ink acceptability, and absorbency. (3) Satin white (Satin white) [Features] Whiteness, glossiness, ink receptivity, improved absorbency, and increased adhesive requirements. (4) Titanium dioxide [Features] Improved opacity and whiteness, expensive. (5) Aminium hydroxide [Features] Improvement in whiteness. (6) Zinc carbide [Features] Improved whiteness, opacity, ink receptivity, and dryness (Gasein formulation). In the paperboard used in the packaging box for a photographic material of the present invention, at least a layer containing at least one of black, gray, and blue dyes or pigments having high opacity is formed on the photographic material side because of the light-shielding property. It is preferred in that respect.

[0148] 2. Adhesive (The main purpose is to bond pigment particles to each other and to adhere them to base paper.) (1) Gasein (Milk casein from Australia and New Zealand) [Features] Natural adhesive, adhesive strength Large, expensive. (2) Soy protein [Features] Extracted from soy, mainly used in the United States. Almost no use in Japan for profitability. (3) Synthetic latex (styrene / butadiene copolymer latex (SBR latex), methyl methacrylate / butadiene copolymer (MBR), acrylic latex / ethylene / vinyl acetate latex) [Features] Most frequently used synthetic adhesive Agent. Improves paint viscosity, water resistance, gloss, smoothness, etc. (4) Polyvinyl alcohol (PVA) [Features] Maximum adhesive strength. However, there are problems such as unstable coating fluidity and insufficient water resistance. (5) Electron beam curable resin At least one type of electron beam curable organic compound having a dimer acid skeleton derived from a dimer of unsaturated higher fatty acid. [Features] Good photographic properties. Excellent printability, especially excellent ink setting. High gloss. Low energy consumption and no pollution.

[0149] 3. 3. Dispersant (mainly for dispersing pigments and controlling paint viscosity. There are sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, and sodium polycarboxylate). 4. Viscosity modifier (mainly for the purpose of improving fluidity, and includes dicimandiamide, urea, sodium alginate, and CMC). 5. Antifoaming agent (mainly for the purpose of foam prevention and foam control, polyglycol fatty acid ester, tributyl phosphate, phosphate ester, silicone, higher alcohol / pine oil). 6. Anti-dusting agent (mainly to prevent calender dusting and improve gloss finish. There are calcium stearate and wax emulsion.) Waterproofing agent (The main purpose is to make the adhesive water resistant. Formalin, melamine resin, glyoxal, sugar, silicate,
Hexamine, urea resins, zinc, aluminum, tin compounds _{(ZnSO 4, Al (SO 4} ) 3 , etc.) 8. Preservatives (mainly to prevent spoilage; pentachlorophenol (PCP), formalin). The solid content of these paints is usually 30 to 80% by weight, preferably 40 to 75% by weight, particularly preferably. Is adjusted to about 50 to 70% by weight. The viscosity of these paints is 50-1
The coating amount is adjusted to 500 CPS, preferably 100 to 1000 CPS, particularly preferably 150 to 900 CPS, and a coating amount of 3 to 60 g is applied to the printing surface of the paperboard using a usual coating device (air knife coater, various blade coaters, gravure coater, etc.). / M ² , preferably 5 to 50 g / m ² ,
Particularly preferably, it is applied so as to be 10 to 40 g / m ² . In order to improve the smoothness, it is finished by various known calenders, for example, a machine calender, a super calender, a gloss calender, a soft compact calender and the like. In particular, when a sheet for high gloss printing is used, it is preferable to use the cast coat method. In particular, it is preferable to use an electron beam curable resin having excellent photographic properties and ink setting properties.

Further, typical specific examples of the packaging material preferably applied to the packaging bag for a collective package of the present invention are described below. The present invention is not limited to these,
There is no restriction on these representatives without exceeding the gist. Below, it is light-shielding and has a moisture permeability of 10 g /
m ² . 24 hours or less, oxygen permeability is 100 cc / m ^2.
Representative examples of packaging materials of 24 hours and 1 atm or less are shown below.

(1) Simultaneous two-layer coextrusion inflation
Light-shielding film 120 μm (titanium oxide 6 wt% λ HDP
E layer 60 μm × carbon black 3 wt%, silica 0.
2 wt%, lubricant 0.1 wt% λL-LDPE layer 60μ
m) (2) K-coated cellophane 20 μm / adhesive layer LDPE 1
5 μm / Al foil 7 μm / L-LDPE 30 wt% λL
DPE coating layer 30μm (3) Al deposition (400Å) ONy film 15μm /
Adhesive layer LDPE 15μm / Simultaneous two-layer coextrusion blown film / light-shielding film 55μm (HDPE layer 25μm ×
(3 wt% λL-LDPE layer 30 μm) (4) K-coated OPP film 20 μm / adhesive layer modified P
O 20 wt% λLDPE 15 μm / carbon black 3 wt%, HDPE 20 wt% λL-LDPE light-shielding film 70 μm (5) Synthetic paper 50 μm / adhesive layer LDPE 15 μm / A
l foil 9μm / EEA 30wt% λLDPE coating layer 35
μm (6) Glassine paper 40 μm / adhesive layer LDPE 15 μm
/ Al foil 9 μm / adhesive layer LDPE 15 μm / barium sulfate 5 wt% λL-LDPE light-shielding film 60 μm (7) Titanium oxide 5 wt% λ biaxially stretched PET film 1
2 μm / adhesive layer LDPE 15 μm / Al foil 7 μm / adhesive layer LDPE 15 μm / titanium oxide 5 wt%, lubricant 0.
2wtλL-LDPE light shielding film 50μm (8) Titanium oxide 5wt% λ biaxially stretched PET film 1
2 μm / adhesive layer LDPE 15 μm / Al deposition (400
Å) ONy film 15 μm / adhesive layer LDPE 15 μm
/ Carbon 3wt%, lubricant 0.1wt%, HDPE 5
wt% λL-LDPE light-shielding film 60 μm (9) Silica 0.2 wt% λ biaxially stretched PET film 1
2 μm / adhesive layer LDPE 15 μm / Al deposition (400
Å) OEVOH 20 μm / adhesive layer LDPE 15 μm
/ Simultaneous two-layer coextrusion blown light-shielding film 60μ
m (carbon 3w HDPE layer 30 μm, fungicide 0.0
5 wt% λ x 0.1 wt% lubricant, 0.2 wt% antifogging agent
(λ, L-LDPE layer 30 μm) (10) Al deposition (400 °) Ony film 15 μm
/ Carbon 3wt%, L-LDPE 20wt% λLD
PE coating layer 60 μm (11) K-coated ONy film 15 μm / carbon 3
wt%, L-LDPE 20 wt% λLDPE coating layer 60
μm (12) K-coated PET film 15 μm / carbon 3
wt%, L-LDPE 20 wt% λLDPE coating layer 60
μm (13) K-coated EVOH film 15 μm / carbon 3 wt%, L-LDPE 20 wt% λLDPE coating layer 6
0μm (14) Al deposition (400Å) LDPE film 30μ
m / Carbon 3wt%, L-LDPE 20wt% λL
DPE coating layer 60μm (15) Al deposition (400Å) CPP film 25μm
/ Carbon 3wt%, L-LDPE 20wt% λLD
PE coating layer 60 μm (16) Lubricant 0.05 wt%, HDPE 20 wt% λ,
Titanium oxide 6wt% λL-LDPE film 50μm /
Adhesive layer LDPE 15μm / Al foil 7μm / Evaporation layer LD
PE 15μm / lubricant 0.05wt%, silica 0.05
wt%, carbon black 3 wt% λ L-LDPE film 50 μm (17) Titanium oxide 6 wt% λ diagonally uniaxially stretched HDPE film 45 μm / adhesive layer LDPE 15 μm / carbon 4.5 wt%, L-LDPE 20 wt λ diagonally uniaxially stretched HDPE film 50 μm (18) ) Synthetic paper 50 μm / adhesive layer LDPE 15 μm /
Al deposited (400Å) ONy film 15μm / adhesive layer LDPE 15μm / lubricant 0.05wt%, HDPE
15 wt% λL-LDPE film 50 μm (19) PET non-woven fabric 70 μm / adhesive layer LDPE 15
μm / Al deposited (400Å) ONy film 15μm /
Adhesive layer LDPE 15μm / lubricant 0.05wt%, HD
PE 15 wt% λL-LDPE film 50 μm (20) Biaxially stretched PET film 12 μm / adhesive layer LD
PE 15μm / Al foil 7μm / adhesive layer / LDPE 1
5 μm / EEA 20 wt% λCPP film 50 μm (21) Biaxially stretched PET film 12 μm / adhesive layer modified PO 20 μm / iron foil 25 μm / adhesive layer modified PO 20
μm / lubricant 0.5 wt%, HDPE 10 wt% λL-
LDPE film 50 μm [Description of abbreviations] wt%; wt% K coat; coating with vinylidene chloride compound LDPE; high-pressure method branched low-density homopolyethylene resin L-LDPE; low-pressure method linear low-density polyethylene resin Al foil; aluminum foil HDPE High density polyethylene resin (including homo and copolymer) ONy; Biaxially stretched nylon resin OPP; Biaxially stretched polypropylene resin EEA; Ethylene ethyl acrylate copolymer PET; Polyethylene terephthalate resin OEVOH; Biaxially stretched ethylene-vinyl acetate copolymer Saponified resin (biaxially stretched ethylene / vinyl alcohol copolymer resin) EVOH; ethylene / vinyl acetate copolymer saponified resin (ethylene / vinyl alcohol copolymer resin) X; Coextrusion Modified PO; unsaturated carboxylic acid or Its anhydride Abbreviation graft-modified polyolefin resin (also referred to as adhesive polyolefin resin)

When the moisture permeability is 10 g / m ² . Representative specific examples of preferred packaging materials applicable to the packaging bag for the translucent or transparent assembly package of the present invention having an oxygen permeability of 100 cc / m ² · 24 hours · 1 atm or less and a haze of 80% or less for 24 hours or less. Examples are given below. It should be noted that the present invention is not limited to these, and is not limited to these representative examples at all without departing from the gist thereof.

(1) Single layer blown film (0.1% by weight of antifogging agent, 0.05% by weight of lubricant, 0.1% by weight of antioxidant, 5% by weight of HDPE, 100 μm of λL-LDPE film) (2) K-coated cellophane 26 μm / adhesive layer LDPE 1
5 μm / L-LDPE 20 wt% λL-LDPE film 80 μm (3) K-coated OPP film 20 μm / adhesive layer LDP
E 15μm / L-LDPE 20wt% λL-LDP
E-film 80 μm (4) K-coated Any 15 μm / adhesive layer LDPE 1
5 μm / 0.05% by weight of antifogging agent, 0.05% by weight of lubricant,
LDPE 10 wt% λL-LDPE film 70 μm (5) Biaxially stretched PET film 12 μm / adhesive layer LDP
E 15 μm / Ony 15 μm / adhesive layer LDPE 15
μm / anti-fog agent 0.1wt%, lubricant 0.05wt%, LD
PE 5wt% λL-LDPE film (6) Biaxially stretched PET film 12μm / adhesive layer LDP
E 15μm / OEVOH 25μm / adhesive layer LDPE
15μm / anti-fog agent 0.1wt%, lubricant 0.05wt
%, LDPE 5wt%, HDPE 5wt% λL-
LDPE film (7) Simultaneous two-layer coextrusion blown film 120
μm (0.1% by weight of anti-fogging agent 50 μm of λHDPE layer × 0.05% by weight of lubricant, 0.1% by weight of anti-fogging agent, 0.1% by weight of silica
(λL-LDPE layer 70 μm) (8) Three-layer co-extrusion blown film 100
μm (lubricant 0.1 wt%, λNy layer 20 μm, modified PO layer 15 μm, anti-fogging agent 0.1%, lubricant 0.1 wt%, antioxidant 0.1 wt%, UV inhibitor 0.05 wt%, HD
PE 10 wt% λL-LDPE layer 65 μm) (9) Four-layer co-extrusion blown film 100 at the same time
μm (lubricant 0.1 wt% λNy layer 15 μm × EVOH layer 20 μm × modified PO layer 15 μm × antifogging agent 0.1 wt
%, Lubricant 0.05 wt% λL-LDPE layer 50μ) (Description of abbreviations) Ny;

In the package, haze (JIS K6)
714) is made transparent to 80 or less, and an antifogging agent is added so that the packaged object can be seen through. Hereinafter, typical examples of the antifogging agent will be described below. (1) Sorbitan surfactant (sorbitan monostearate, sorbitan monopalmitate, sorbitan monobenzoate, etc.) (2) Glycerin surfactant (glycerin monolaurate, diglycerin monopalmitate, glycerin monostearate, etc.) (3) Polyethylene glycol-based surfactants (polyethylene glycol monostearate, polyethylene glycol monopalmitate, etc.) (4) Those obtained by adding alkylene oxide to the above-mentioned surfactants (alkylphenol / formalin condensate, benzylated phenol / formalin) Condensate, N, N-bis (2-hydroxyethyl) fatty acid amide, N, N-bis (2-hydroxyethyl) stearylamine, polyoxyethylene sorbitan fatty acid partial ester, alkylbenzenes Hong salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ether. The addition amount is 0.01 to 5 wt%, preferably 0.05
To 3% by weight, particularly preferably 0.1 to 2% by weight.

The packaging bag for a collective package of the present invention is JIS Z 0 irrespective of whether it is light-shielding or translucent or transparent.
The water vapor transmission rate (= water vapor transmission rate) by the cup method of 208 is 1
0 g / m ² · 24 hours or less, preferably 5 g / m ² · 2
ASTM D 3985 (Modern Co., USA) for 4 hours or less, particularly preferably 1 g / m ² · 24 hours or less.
ntol Co. Oxtran instrument used) oxygen permeability measured at (20 ° C · 0% RH ) is 100cc / m ² · ²
The pressure is 4 hours / atmosphere or less, preferably 50 cc / m ² · 24 hours or less, particularly preferably 25 cc / m ² · 24 hours / atmosphere or less.

A particularly preferred antioxidant is a phenolic antioxidant, and commercially available products include various types of Irganox manufactured by Ciba Geigy (typically, Ireganox).
1010, Ireganox 1076, etc.) and Sumitizer BH-T, Sumiliz of Sumitomo Chemical Co., Ltd.
er BH-76, Sumilizer WX-R, S
umilizer BP-101 and the like. Also, 2.
6-di-butyl-p-cresol (BHT), a low volatility, high molecular weight phenolic antioxidant (trade name Ireg)
anox 1010, Ireganox 1076, T
opanol CA, Ionox 330, etc.), diuraryl thiodipropionate, distearyl thiopropionate, dialkyl phosphate, etc.
It is effective to use more than one species in combination.

It is preferable to use a phenolic antioxidant and a phosphorus antioxidant in combination with carbon black since the antioxidant effect is particularly exhibited. Other plastic data
Handbook (published by KK Industrial Research Council) 794-799
Various antioxidants and plastic additives disclosed on pages 327 to 329 of the collection of data on various antioxidants and plastic additives (KK Chemical Industry Co., Ltd.)
GE ENCYCLOPEDIA Progress 1986 (K
It is possible to select and use various antioxidants disclosed on pages 211-212 of K Plastic Age). As a combination of two or more antioxidants,
For example, a combination of a hindered phenolic antioxidant and a pentaerythritol phosphite compound-based antioxidant, a combination of a hindered phenolic antioxidant and a diorganopentaerythritol diphosphite compound-based antioxidant, Alkyl-substituted monophenolic antioxidants, alkyl-substituted polyhydric phenolic antioxidants, organic phosphite compound-based antioxidants, and organic phosphorus phosphides, such as combinations of phenolic antioxidants and phosphite antioxidants There is an acid ester-based antioxidant or one selected from any of these or a combination of two or more thereof. Among these, hindered antioxidants can prevent thermal degradation of zinc stearate, which is susceptible to thermal degradation, not only can significantly reduce the occurrence of bumps, but also improve the photographic properties of photographic photosensitive materials. It is particularly preferred because it can be converted to

The light-shielding substance which is one of the essential components of the present invention is shown below. 1. Inorganic compounds A. Oxides: silica, diatomaceous earth, alumina, titanium oxide, iron oxide (iron black), zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, alumina fiber, etc. Hydroxide: aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate Carbonate; calcium carbonate, magnesium carbonate, dolomite, dawsonite, etc. (Sulfite): calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, etc. Silicates; talc, clay, mica, asbestos,
F. Glass fiber, glass balloon, glass beads, calcium silicate, montmorillonite, bentonite, etc. Carbon; carbon black, graphite, carbon fiber, carbon hollow sphere, etc. Others: iron powder, copper powder, lead powder, aluminum powder, molybdenum sulfide, polon fiber, silicon carbide fiber, brass fiber,
Potassium titanate, lead zirconate titanate, zinc borate, barium metaborate, calcium borate, sodium borate, aluminum paste, talc, etc.

[0159] 2. Organic compounds Wood flour (pine, oak, sawdust, etc.), shell fiber (almond, peanut, fir shell, etc.), cotton, jute, paper strip, cellophane strip, nylon fiber, polypropylene fiber,
Starch (including modified starch and surface-treated starch),
Aromatic polyamide fiber, etc.

Of these light-shielding substances, inorganic compounds which make opaque are preferable since they hardly adversely affect photographic properties and are stable to heat even at 150 ° C. or higher, and are particularly excellent in heat resistance and light resistance. Since it is an inert substance, light-absorbing carbon black, titanium nitride, graphite and iron black are preferred.

Examples of classification of carbon black raw materials include gas black, furnace black, channel black, anthra black, acetylene black, Ketchen carbon black, thermal black, lamp black, oil smoke, pine smoke, animal black, vegetable black, and the like. There is.

The P case used in the above-described embodiment has a cylindrical shape. However, the present invention is not limited to this. For example, an elliptical cylindrical shape (Japanese Patent Laid-Open No. 6-2759).
No. 3, JP-A No. 7-168321), a square tube shape (Japanese Utility Model Laid-Open No. 1-113235, etc.), and an elliptical tube shape containing two photographic photosensitive material storage magazines (Japanese Utility Model No.
-48581) and the like. Further, the present invention relates to 4
It may be used to package a sheet film pack containing a plurality of × 5 inch sheet films.

[0163]

As described above, in the photographic light-sensitive material assembly package of the present invention, a plurality of photographic light-sensitive material storage magazines each stored in a moisture-proof case are used as a heat-sealing layer for a low-density homopolyethylene resin. And / or a polyolefin resin layer having an ethylene resin layer containing 5% by weight or more of an ethylene copolymer resin and having a thickness of 20 to 7
Since the sleeve is integrally packaged with a 0 μm vertically uniaxially stretched multi-layer laminated film, it is inexpensive and does not adversely affect the photographic properties of photographic light-sensitive materials, while improving transparency, low-temperature sealing, high-speed packaging, recycling, and incineration. it can.

Further, when the ethylene-based resin layer is provided on both sides of the high Young's modulus polyolefin resin layer, the thickness is 20 to 7%.
Since the sleeve is integrally packaged with a 0 μm longitudinally uniaxially stretched multilayer laminated film, in addition to the above effects, the film moldability can be improved, the suitability for packaging can be improved, and the low-temperature heat sealability and aging heat sealability can be improved. The heat seal layer has a density of 0.870 to 0.935 g / cm.
3 ethylene-α olefin copolymer resin 5 to 99.9
89% by weight, lubricant 0.01 to 10% by weight, phosphorus-based phenolic antioxidant and / or antioxidant 0.001 to 0.001%
Since 1% by weight is included, the drop strength can be improved in addition to the above effects. Further, A
The thickness having a high Young's modulus polyolefin resin layer of 6000 kg / cm ² measured by STMD638 is 20 to 7
Since the sleeve is integrally packaged with a 0 μm vertically uniaxially stretched multilayer laminated film, the same effects as described above can be obtained.

Further, since the photographic light-sensitive material collective package is stored in the moisture-proof bag with printing, the moisture-proof property can be further improved and the appearance can be improved. Further, since the photographic light-sensitive material collective packaging body is housed in an easy-opening decorative box made of a coated printing paper having a coating layer on at least the printing surface side of a laminated paperboard having two or more layers, the opening is easy and the appearance is improved. Can be improved, and the appearance, printing suitability, printing workability and processing suitability can be improved. In addition, the surface of the easy-opening decorative box is formed from the surface side of two or more laminated paperboards with a coating layer, a printing layer,
Since the processing is performed in the order of the overprint varnish, the appearance, printability, printing workability and workability can be improved, and scratch resistance, non-slip properties, and discoloration can be prevented.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a layer structure of a shrink film used for a collective package of the present invention.

FIG. 2 is a sectional view showing a layer structure of a two-layer co-extruded film.

FIG. 3 is a sectional view of a P case accommodating a photo film cartridge.

FIG. 4 is an external view of a collective package.

FIG. 5 is an external view showing an embodiment in which a collective package is stored in a moisture-proof bag.

FIG. 6 is a schematic sectional view showing a layer configuration of a moisture-proof packaging bag.

FIG. 7 is an explanatory view showing a collective package housed in an easy-open packaging box.

FIG. 8 is an explanatory view showing another easy-open packaging cosmetic box.

FIG. 9 is an explanatory view showing a collective package housed in a hanging easy-open packaging box.

[Explanation of symbols]

 1, 26 Collective package 2 P case 3 Photo film patrone 4 Case body 7 Shrink film 11 Middle layer 12 Upper layer 13 Lower layer 15 Double-layer co-extrusion film 28 Packaging bag 38, 40, 42 Easy-opening cosmetic box

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03C 3/00 560 G03C 3/00 560Q 565 565G 565V 570 570M 585 585C B65D 81/24 B65D 81/24 F

Claims (7)

[Claims] 1. A heat-sealing layer comprising a plurality of magazines each containing a photographic photosensitive material housed in a moisture-proof case, an ethylene-based resin layer containing 5% by weight or more of a low-density homopolyethylene resin and / or an ethylene copolymer resin. The thickness consisting of only the provided polyolefin resin layer is 20 to 70 μm
A photographic light-sensitive material assembly package, which is integrally sleeve-wrapped with the vertically uniaxially stretched multilayer laminated film of the above. 2. The method according to claim 1, wherein the ethylene resin layer is formed of ASTM D63.
The thickness provided on both sides of the high Young's modulus polyolefin resin layer whose value measured in 8 is 6000 kgf / cm ² or more is 20
The photographic light-sensitive material assembly package according to claim 1, wherein a sleeve is integrally packaged with a vertically uniaxially stretched multilayer laminated film having a thickness of from 70 to 70 µm. 3. The heat seal layer has a density of 0.87.
5 to 99.989% by weight of ethylene-α-olefin copolymer resin of 0 to 0.935 g / cm 3, 0.01 to 1 of lubricant
The photographic light-sensitive material assembly package according to claim 1, further comprising 0 to 1% by weight, 0.001 to 1% by weight of a phenolic antioxidant and / or a phosphorus-based antioxidant. 4. An ASTM D outside the heat seal layer
The thickness provided with the high Young's modulus polyolefin resin layer having a value measured at 638 of 6000 kgf / cm ² or more is 20 to
4. The photographic light-sensitive material assembly package according to claim 3, wherein the photographic light-sensitive material assembly package is integrally sleeve-wrapped with a 70 [mu] m vertically uniaxially stretched multilayer laminated film. 5. The photographic light-sensitive material assembly package according to claim 1, which is stored in a printed moisture-proof bag having a moisture permeability of 10 g / m ² · 24 hours or less according to a cup method of JISZ0208. Photographic photosensitive material package. 6. An easy-open property comprising a coated printing paper having a coating layer on at least a printing surface side of a laminated paperboard of two or more layers of the photographic light-sensitive material assembly package according to any one of claims 1 to 4. A photographic light-sensitive material assembly package characterized by being housed in a decorative box. 7. The surface of the easy-opening decorative box is processed in the order of a coating layer, a printing layer, and an overprint varnish from the surface side of two or more laminated paperboards. Item 7. A photographic light-sensitive material assembly package according to Item 6.