JP2000206650A - Packaging material for photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a packaging material for a photographic sensitive material having high physical strength, good moisture-proof property and good heat sealability without laminating expensive aluminum foil unsuitable for incineration by using two or more layers including a biodegradable polymer film layer having a specified moisture permeability. SOLUTION: The packaging material consists of two or more layers including a biodegradable polymer film layer 2 which has <=10 g/m2.24 hr moisture permeability (condition B of JIS Z 0208). In the case of >10 g/m2.24 hr moisture permeability, good photographic properties of a packaging photographic sensitive material may not be retrained. The biodegradable polymer film layer 2 must be formed in >=50% thickness proportion to the total thickness because problem on disposal occurs in the case of <50% thickness proportion to the total thickness. Another layer is biodegradable paper substrate 1 comprising natural pulp or biodegradable polymer pulp.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging material for a photographic material having a biodegradable polymer film layer and having no adverse effect on the photographic properties of the photographic material.

[0002]

2. Description of the Related Art Various packaging materials have been proposed as packaging materials for photographic photosensitive materials for packaging photographic papers, photographic films and the like (including black and white and color negatives, positive and reversal, and diffusion transfer). For example, Jiko 61-20
No. 590 discloses that an HDPE resin film containing carbon black is uniaxially stretched at a stretching ratio of 2.2 to 4.2 times.
There has been proposed a cross-laminated film in which two or more layers are stretched at an angle of 45 to 90 degrees.

Japanese Patent Publication No. 2-2700 discloses that an ethylene / α-olefin copolymer resin is composed of a polyethylene-based polymer and 1% by weight or more of a light-shielding substance, and 50% by weight or more of the total polyethylene-based polymer. A photosensitive material packaging film having at least one light-shielding film has been proposed.

Japanese Utility Model Publication No. 2-19226 discloses that an anchor coat layer is formed on an inner light-shielding heat-sealing film layer containing a lubricant, a light-shielding substance and 50% by weight or more of an LDPE resin, and the aluminum foil has a peel strength of 400 g. / 15m
Packaging materials laminated with a width of m or more have been proposed.

Japanese Patent Publication No. 63-26697 discloses that from the outside, a PET layer / aluminum layer / a PO-based resin layer containing a light-shielding material and a nonionic antistatic agent has an optical density of 7.5 or more. Packaging materials have been proposed.

[0006]

However, the above-mentioned conventional packaging materials do not have all functions sufficiently as packaging materials for photographic light-sensitive materials, and each has problems. That is, the packaging material proposed in Japanese Utility Model Publication No. 61-20590 is expensive and has insufficient antistatic properties, heat sealing suitability, and moisture proof properties.

[0007] The photosensitive material packaging film proposed in Japanese Patent Publication No. 2-2700 is insufficient in antistatic properties, moisture proof properties, oxygen barrier properties and Young's modulus. If it is laminated and covered, it is expensive and there is a problem in incineration.

[0008] The packaging material proposed in Japanese Utility Model Publication No. 2-19226 has insufficient photographic properties, physical strength, and hermetic sealing properties, and has a problem in incineration.

The packaging material proposed in Japanese Patent Publication No. 63-26697 is expensive, has anti-blocking properties, photographic properties,
The sealability and physical strength by heat sealing were insufficient, and there was a problem in incineration.

Although the homopolyethylene resin alone is insufficient in the sealing property by heat sealing (especially after a lapse of one month or more), when a light-shielding substance is contained, the sealing property is further deteriorated, and the lubricant, the charge When bleed-out additives such as an antioxidant and an antioxidant were contained, it was impossible to ensure complete sealing by heat sealing. Furthermore, the aluminum foil, by annealing the rolling oil used during rolling,
It was difficult to completely remove it, and the photographic properties deteriorated.

As described above, the present invention can provide various characteristics required as a packaging material for photographic light-sensitive materials, in which conventional packaging materials were insufficient. That is, an object of the present invention is to provide a packaging material for photographic light-sensitive materials having high physical strength, good moisture-proof properties, good heat-sealing properties, etc., without laminating an expensive aluminum foil having a problem in incineration.

[0012]

The packaging material for a photographic light-sensitive material according to the present invention comprises two or more layers, at least one of which is a biodegradable polymer film layer and has a water vapor permeability ( conditions of JIS Z 0208 B) is 10g / m ² · ²
It is configured to be less than 4 hours.

In the packaging material for a photographic light-sensitive material according to the present invention, the biodegradable biopolymer film layer has good disposability and maintains good physical strength, moisture-proof property, heat-sealing property and the like. . In addition, the moisture permeability (JIS Z 02
08) is set to 10 g / m ² · 24 hours or less, so that the sensitizing dye, the coloring dye and the like in the photographic photosensitive layer are not deteriorated by humidity, and the photographic properties are not adversely affected. In addition, gelatin, which is a main component of the back layer and the photographic photosensitive layer, absorbs moisture and has tackiness to prevent occurrence of blocking failure.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The packaging material for photographic light-sensitive material of the present invention comprises two or more layers, and at least one of the layers is provided.
The layer is composed of a biodegradable biopolymer film layer. As the biodegradable polymer constituting the biodegradable biopolymer film layer, various known biodegradable polymers can be used. Among them, 3-hydroxybutyrate-3-
Hydroxyvalerate copolymer, polybutylene succinate resin, polybutylene succinate adipate resin, polylactic acid resin, biodegradable polyester resin, biodegradable composite polymer consisting of fine cellulose fiber and chitosan and protein, ester bond Introduced vinyl resin, aliphatic polyurethane resin containing ester bond, polyvinyl alcohol, aliphatic polyester resin made from fermented lactic acid, etc., poly-3-hydroxybutyric acid resin, copolymer resin of aliphatic polyester and polyamide, Polycaprolactone resin with crystallinity of 40% or less, heat-composite polymer of carboxymethylcellulose and chitosan, blend resin of general-purpose resin (polyethylene resin, polypropylene resin, polystyrene resin) and aliphatic polyester resin, crystallinity Is 50% Lower poly-3-hydroxybutyric acid polymer, cellulose acetate resin, starch-containing thermoplastic resin, compound having two or more functional groups capable of reacting with chitosan and polyvinyl alcohol and amino group or hydroxyl group, starch and chitosan salt heated gel An aliphatic polyester resin having a polymerized mixture-containing polymer, a hydroxycarboxylic acid and / or an aliphatic polyhydric alcohol and an aliphatic polybasic acid as a polymerization component is preferred.

A particularly preferred method for producing an aliphatic polyester resin is not particularly limited. For example, lactic acid, lactic acid and a hydroxycarboxylic acid other than lactic acid, or aliphatic diol and an aliphatic dicarboxylic acid are added to an organic solvent and a catalyst. The weight-average molecular weight obtained by direct dehydration condensation under direct dehydration condensation is as high as 16,000,000, preferably 2-5,000,000, more preferably 3-4,000,000, particularly preferably 4-2,000,000, and most preferably 5-1,000,000. Is a molecule.

Particularly preferably, among aliphatic polyester resins, polylactic acid, a copolymer resin containing lactic acid and a hydroxycarboxylic acid other than lactic acid as a polymerization component, lactic acid and an aliphatic polyhydric alcohol and an aliphatic polybasic acid are used. Resin containing polylactic acid as a polymerization component, polylactic acid and 3-hydroxybutyrate-3
A blend resin with a hydroxyvalerate copolymer resin, a polycaprolactone resin having a crystallinity of 40% or less, and most preferably a lactic acid component content of 30% by weight.
It is a polymer containing the above aliphatic polyester resin.

Table 1 shows typical examples of polymer materials which are currently being marketed or commercialized for biodegradable polymer films.

[0018]

[Table 1]

The content of the biodegradable polymer is 50% by weight or more, preferably 60% by weight or more, more preferably 7% by weight.
It is at least 0% by weight, most preferably at least 80% by weight.
If the content is less than 50% by weight, it may not be sufficiently decomposed at the time of disposal.

The moisture permeability of the packaging material for photographic light-sensitive materials of the present invention
(Condition B of JIS Z 0208) is 10 g / m ² · 24
Time or less, preferably 8g / m ² · 24 hours or less, more preferably 6g / m ² · 24 hours or less, particularly preferably 5g / m ² · 24 hours or less, and most preferably 4g / m ² ·
24 hours or less. If the moisture permeability exceeds 10 g / m ² · 24 hours, the photographic properties of the packaged photographic light-sensitive material may not be able to be maintained well.

The biodegradable polymer film layer is required to be 50% or more of the total thickness of the packaging material for photographic light-sensitive materials.
% Or more, more preferably 80% or more, and 90% or more.
The above is most preferred. If the total thickness is less than 50%, there may be a problem in disposal.

It is preferable that, of the two or more layers, the layers other than the biodegradable polymer film layer are formed of a biodegradable paper base made of natural pulp or biodegradable polymer pulp. By forming with such a biodegradable paper base material, the disposability is further improved.

The natural pulp forming the biodegradable paper base includes wood pulp and non-wood pulp, preferably mixed pulp of softwood pulp and hardwood pulp, and eucalyptus pulp and non-wood pulp with fast growth, particularly preferably pH 5
~ 9 neutral kraft and eucalyptus pulp or non-wood pulp, most preferably non-wood pulp.

As the biodegradable polymer pulp, there is one obtained by pulping the biodegradable polymer.

Since natural pulp also has biodegradability, the biodegradable paper substrate of the present invention has excellent recyclability, biodegradability, and various characteristics, and can reduce CO ₂ gas that causes global warming. Paper with wood pulp is most preferred. The raw materials for this non-wood pulp are kenaf, bagasse,
Straw, bamboo, corn stalks, sugar cane, papyrus, troloi, sycamore, okra, sorghum, apaca, cannabis, manila hemp, sisal hemp, linter, beer squeeze, and the like. It is a non-wood paper made from kenaf or bagasse which is fast growing, has good mass productivity, and has various excellent properties, and has a thickness of 7 to 250 μm, preferably 10 to 200 μm.
Particularly preferred is a biodegradable paper substrate of 15 to 150 μm in the present invention.

Of the two or more layers, the layers other than the biodegradable polymer film layer are biodegradable polymer film layers, and these two biodegradable polymer film layers are formed by co-extrusion. That is, it is preferable that the film is formed of a two-layer co-extruded film of a biodegradable polymer film layer. By forming with such a two-layer co-extruded film, compared to the case where a biodegradable paper base material is laminated,
Moisture resistance, physical strength, and the like can be further improved.

The two biodegradable polymer film layers formed by the two-layer coextrusion may be formed of the same resin composition or different resin compositions. That is, the layer located on the photographic material side is required to have a heat-sealing property without adversely affecting the photographic material, and the layer located on the outside is required to have physical strength and the like. It is preferable to design the resin composition according to the characteristics.

In the two or more layers, the layers other than the biodegradable polymer film layer contain 5% by weight of the ethylene copolymer resin.
Or more, preferably 10% by weight or more, more preferably 20% by weight or more.
It is preferable that the thermoplastic resin film layer contains at least 40% by weight, particularly preferably at least 40% by weight, most preferably at least 50% by weight, and has heat sealability.
By forming with a thermoplastic resin film layer containing such an L-LDPE resin, it is less expensive than a two-layer co-extruded film of a biodegradable polymer film layer, and has a physical strength and
Film formability and the like can be further improved.

Examples of the ethylene copolymer resin include random and block copolymer resins of ethylene and α-olefin, ethylene / acrylic acid copolymer resin, ethylene / methyl methacrylate copolymer resin, ethylene / acrylate ester There are a copolymer resin, an ethylene-vinyl acetate copolymer resin, an ionomer resin and the like.

Examples of copolymer resins obtained by polymerizing ethylene and α-olefin using a Ziegler catalyst include LL
There is DPE resin. This L-LDPE ( L inear L
ow D ensity Poly e thylene) resin is called third polyethylene resin, medium low-pressure process, energy conservation has both the advantages of high-pressure two polyethylene resins, low cost to meet the needs of the times that resource saving, high-strength resin It is. This resin is obtained by copolymerizing ethylene with an α-olefin having 3 to 20, preferably 3 to 12, particularly preferably 4 to 8, and most preferably 6 to 8 carbon atoms by a low pressure method or a high pressure improvement method. It is a polyethylene resin having a structure in which a linear linear chain has short branches. Preferred α-olefins in terms of physical strength and cost include propylene, butene-1, 3-methylpentene-1, and pentene-
1, hexene-1, 4-methylpentene-1, octene-1, nonene-1, decene-1, pentadecene-1, octadecene-1, eicosene-1 and the like are used. In particular, ethylene / α-olefin having 4 to 8 carbon atoms
Although an α-olefin random copolymer resin is preferred in the present invention, an ethylene / α-olefin block copolymer resin or a mixed resin of these two types can also be used.

Typical polymerization processes of L-LDPE resins include a gas phase method using a medium / low pressure apparatus, a solution method, a liquid phase slurry method, and a high pressure improvement method using a Ziegler catalyst at a high temperature and a high pressure. There is a high pressure conversion method for obtaining an LDPE resin.

Typical specific examples of L-LDPE resins produced by polymerization using a commercially available multi-site catalyst are shown below. (1) Ethylene / butene-1 copolymer resin G resin (UCC) Dourex (Dow Chemical) Screer (DuPont Canada) Marrex (Philips) Stamirex (DSM) Sumikasen L (Sumitomo Chemical) Neozex (Mitsui Petrochemical) Novatec-L (Mitsubishi Kasei) Yucaron-LL (Mitsubishi Yuka) Nisseki Linirex (Nippon Petrochemical) Shorex Linear (Showa Denko) NUC Polyethylene-LL (Nippon Unicar) Ube Polyethylene L (Ube Industries) Idemitsu Polyethylene L (Idemitsu Petrochemical) Nipolon L (Tosoh) (2) Ethylene-hexene-1 copolymer resin Exelene VL (Sumitomo Chemical) TUFLIN (UCC) NUC-FLX (Nack Flex) (UCC) TUFTHENE ( Nippon Unicar) Nipolon (Tosoh) (3) Ethylene / 4-methylpentene-1 copolymer resin Ultoxex (Mitsui Petrochemical) (4) Ethylene / octene-1 copolymer resin Stamilex (DSM) Dourex (Dow Chemical) Screa (Dupont Canada) MORETEC (Idemitsu Petrochemical)

Among these L-LDPE resins, a resin preferable for use in a wrapping material for a photographic light-sensitive material particularly requiring a tear strength and an impact piercing strength has a melt flow rate (hereinafter referred to as MFR) of 0. .1-40g / 10
Min (measured under condition 4 of JIS K-7210. Test temperature 1
90 ° C, test load 2.16kgf), density 0.870-
0.940 g / cm ³ (JIS K-7112), and the number of carbon atoms of the α-olefin is 3 to 15, preferably 4 to
Ten, particularly preferably six to eight, are obtained by a liquid phase process and a gas phase process. In addition, Sumikasen-L (Sumitomo Chemical), Nipolon L (Tosoh), Ubepolyethylene L (Ube Industries), and the like obtained by an improved high-pressure process in which equipment costs are reduced by using a conventional high-pressure process.
-LDPE resins are also preferred.

A typical example having a high physical strength and a preferable representative name is a trade name. 4-methylpentene-1 having 6 carbon atoms as an α-olefin side chain was introduced into polyethylene by polymerization using a multi-site catalyst. Idemitsu Petrochemical Co., Ltd. introduced by Mitsui Petrochemical Co., Ltd. with Ultrazex and octene-1 having 8 carbon atoms as an α-olefin side chain.
MORETEC, Stamirex from DSM, and Dourex from Dow Chemical (all L-LDPE resins obtained by a liquid phase process in all four companies). Preferred representative examples obtained by the low-pressure gas phase process are listed below under trade names.
TEX of Nippon Unicar Co., Ltd. which introduced hexene-1
THEN and TUFLIN of UCC.

The recently released density is 0.910 g
/ Cm ³ ultra low density linear low density polyethylene resin such as NUC-FLX of UCC or Sumitomo Chemical Co., Ltd.
(The above two companies use hexene-1 whose α-olefin has 6 carbon atoms).

The outline of the features of the production process of L-LDPE resin using a multi-site catalyst and the trade names of the respective resin manufacturers are shown below.

The relationship between the outline of a typical production process and the trade name of each resin manufacturer will be described below.

[1] Gas-phase method It is reported that the amount of energy required for polymerization is small.
In terms of quality, it is necessary to use a single component that is easy to volatilize as a comonomer, which is limited compared to the solution method. In recent years, it seems that the selection range of the comonomer and the control range of the molecular weight distribution are also increasing.

[2] Slurry method The liquid phase polymerization method using a solvent is classified into a slurry method and a solution method. In the slurry method, a solvent is used, but a slurry (heterophase type) is used. Therefore, since the solution in the reaction vessel has a low viscosity, it can be produced with relatively compact equipment, and the solvent can be easily removed. There are advantages. On the other hand, regarding low density, the low molecular weight low density polymer dissolves in the solvent, the solution becomes high in viscosity, or the polymer expands and agglomerates, so that the LL having a density of 0.930 g / cm ³ or less is used.
DPE production is limited.

[3] Solution Method Polymerization in the solution method is performed in a solution. The reaction is performed at a high temperature to maintain a solution state. In terms of quality, the permissible range for lowering the density is wide, and C ₆ or more α-olefins (butene-1, pentene-1,4-methylhexene-1,4,4
-Dimethylpentene-1, 4-methylpentene-1, hexene-1, heptene-1, octene-1, decene-1,
It is an optimal production process for the polymerization of ethylene with eicosene-1, dodecene-1, hexadecene-1, octadecene-1, tetradecene-1 and the like. Further, L-LDPE resin having a large α-olefin content (having a density of 0.910 g /
It is also optimal as a manufacturing process for an ultra-low density L-LDPE resin (cm ³ or less).

[4] Improved high-pressure method A method for obtaining an L-LDPE resin at a high temperature and a high pressure with a Ziegler-based melting medium while using the conventional high-pressure method as it is, and the running cost is higher than that of the above-mentioned gas-phase method, slurry method and solution method. It is. Also called high pressure conversion method.

[Outline of the above manufacturing process] Solution method: pressure: 450 to 650 PSi, temperature: 20
0 to 250 ° C. Slurry method: pressure: 400 to 500 PSi, temperature: 90
-100 ° C Gas phase method: pressure: 250-350PSi, temperature: 90
-100 ° C Improved high pressure method: Pressure: about 20,000 PSi, temperature: 2
Around 00 ℃

The ratio of ethylene to α-olefin is preferably 60% by weight or more and 70% by weight or more, more preferably 80% by weight or more. 60 ethylene
When the amount is less than 10% by weight, the polymerization suitability is deteriorated and the cost is high, and the obtained ethylene / α-olefin copolymer resin has large tackiness, and the film moldability is deteriorated, and the blocking between the films is large, It is difficult to put it to practical use except for using it as a blocking laminated film.

As the resin other than the ethylene copolymer resin that can be used for the thermoplastic resin film layer, there are various thermoplastic resins. In particular, forming a polyolefin resin as a main component is excellent in recyclability and incineration suitability. It is preferable because it is inexpensive, has good photographic properties, and has excellent physical strength and moisture resistance.

Examples of polyolefin resins include the above-mentioned ethylene copolymer resins, homopolyethylene resins, homopolypropylene resins, random and block copolymer resins of propylene and α-olefin, acid-modified polyolefin resins, ionomer resins, polyolefin resins. And the like.

As the homopolyethylene resin, a radical initiator such as oxygen or peroxide may be used.
Branched low-density homopolyethylene resin having a long-chain branching density of 0.910 to 0.925 g / cm ³ , produced by a method of polymerizing ethylene at a temperature of 1000 ° C. and a temperature and pressure of 1000 to 3000 kg / cm ^2. And a method of polymerizing ethylene under the conditions of 50-250 ° C. and 50-200 kg / cm ² using a medium / low pressure Ziegler catalyst (Ti system) or a Phillips catalyst (Cr system). ,
A high-density homopolyethylene resin having a linear density of 0.941 to 0.985 g / cm ³ can be obtained by a high-pressure method or a medium / low-pressure method. density being manufactured Te there is a density homopolyethylene resin in the 0.926~0.940g / cm ^3.

Further, there is a homopolyethylene resin of various densities having a reduced molecular weight distribution and a reduced composition distribution produced by polymerization using a metal metallocene polymerization catalyst, which is a kind of single-site catalyst, which has recently been put into practical use as a main component. This single-site catalyst can be used in the same manner or partially modified as the single-site catalyst described below.

As the homopolypropylene resin, a Ziegler catalyst (Ti-based) is mainly used.
A resin produced by polymerizing propylene at a temperature and pressure of 35 kg / cm ² and having a density of 0.890 to 0.910 g / cm ³ . Generally, it is an isotactic resin obtained by polymerizing propylene in the presence of a solvent using an aluminum alkyl / titanium tetrachloride Ziegler-Natta catalyst. A polypropylene resin produced by polymerization using a metallocene catalyst, which is one of the recently discussed single-site catalysts, is particularly preferable because of its excellent photographic properties and physical properties.

Examples of the copolymer resin of propylene and α-olefin include propylene / ethylene random copolymer resin, propylene / ethylene block copolymer resin, propylene / butene-1 random copolymer resin, and propylene / butene- 1-block copolymer resin, propylene / ethylene / butene-1 terpolymer resin, propylene / ethylene / diene terpolymer resin, propylene / hexene-1 random copolymer resin, propylene / hexene-
There is a one-block copolymer resin or the like. The amount of the α-olefin is 0.5 to 30% by weight, preferably 1 to 20% by weight, from the viewpoint of the balance between rigidity, physical strength and production suitability.

The α-olefin in the copolymer resin of propylene and α-olefin is the same as the α-olefin in the case of the copolymer of ethylene and α-olefin.

When the above-mentioned polyolefin resin is polymerized, it is preferable to use a polymerization catalyst containing a halogen compound or a metal compound since the amount of the polymerization catalyst having a large adverse effect on the photographic light-sensitive material can be reduced. Representative examples of the polymerization catalyst containing a halogen compound and / or a metal compound include a Ziegler catalyst of a black precipitate obtained when titanium tetrachloride and triethylaluminum are mixed in anhydrous hexane, and titanium trichloride and triethylaluminum in anhydrous hexane. A Ziegler-Natta catalyst of black precipitate obtained by mixing in water, an organic alkyl compound of various metals of groups I, II and III and a metal salt of group IV, V, VI and VII Regular polymerization catalyst, Natta catalyst comprising a mixture of trialkylaluminum and titanium trichloride, SiO ₂ −
A Philips catalyst comprising a mixture of an Al ₂ O ₃ system and chromium oxide, a catalyst comprising a reaction product of a magnesium compound and a titanium halide, and an organic aluminum as a component, and the like.

As a specific example, there is a catalyst using an organic aluminum compound as a cocatalyst with a solid catalyst component which is a reaction product of an oxygen-containing organic compound of magnesium, an oxygen-containing organic compound of titanium, and an aluminum halide compound.

Specific examples of the organoaluminum compound include triethylaluminum, triisobutylaluminum, tri-n-propylaluminum, diethylaluminum monochloride, diethylaluminum monobromide and the like. TiCl ₄ , T
iBr, titanium tetrahalide such as TiI ₄ , Ti (O
_{CH 3) Cl 3, Ti (} OC 2 H 5) trihalide alkoxy titanium ₃ such _{Cl, Ti (OCH 3) 2} Cl 2, Ti (OC 2
_{H 5) 2 Cl 2, Ti} ( dihalogenated alkoxy titanium such as _{OC 2 H 5) 2 Br 2} , Ti (OCH 3) 3 Cl, Ti (OC 2 H 5)
There are monohalogenated trialkoxy titanium such as ₃ Cl and Ti (OC ₂ H ₅ ) ₃ Br.

Examples of the organomagnesium compound include ethylbutylmagnesium, diisobutylmagnesium, dihexylmagnesium, ethylmagnesium chloride, MgF ₂ , MgCl ₂ , MgBr ₂ , and MgI ₂ . As a vanadium compound, vanadium tetrachloride, vanadium oxytrichloride, diethoxymonochloride vanadate,
And vanadate diethoxy dichloride. These halogen compounds and / or metal compounds adversely affect the photographic properties of silver halide photographic light-sensitive materials, but the total of fatty acid metal salts and / or zeolites and / or hydrotalcite compounds is 0.01 to 10% by weight, Preferably 0.0
Detoxification can be achieved by adding 5 to 7% by weight, particularly preferably 0.1 to 5% by weight.

When the thermoplastic resin film layer is formed of only a polypropylene resin, the molecular weight distribution is preferably in the range of 1.5 to 1.5.
7.0 is preferable, and 2.0 to 6.5 is more preferable.
2.5-6.0 is most preferred. 1.5 molecular weight distribution
If it is less than 1, the fluidity of the resin deteriorates and molding failure frequently occurs. On the other hand, if the molecular weight distribution exceeds 7.0, the dimensional accuracy deteriorates and the physical strength also decreases. In addition, MFR (AS
The test temperature of 230 ° C. and the test load of 2.16 kgf under the L condition of TM D1238 is preferably 0.01 to 70 g / 10 min, more preferably 0.02 to 50 g / 10 min,
Most preferably, it is 0.03 to 40 g / 10 minutes,
If it is less than 01 g / 10 minutes, the fluidity of the resin is poor, melt fracture frequently occurs, and it cannot be put to practical use. The melt flow rate is 70 g /
If it exceeds 10 minutes, the fluidity of the resin becomes too large, the film formability deteriorates, and the physical strength is too small to be practically used.

The most preferred polyolefin resin is a single-site catalyst (a typical example is a metallocene catalyst).
It is produced by polymerization using

L-LDPE resins produced by polymerization using a single-site catalyst include zirconium-based, titanium-based,
Copolymer resin of ethylene having a molecular weight distribution of 1.5 to 10 and an α-olefin having 3 to 12 carbon atoms produced by polymerization using a single-site catalyst containing at least one of a hafnium-based and a vanadium-based metallocene complex. It is preferable that the material is excellent in physical strength, has little residual metal component and residual halogen-based compound component, has little adverse effect on photographic properties of photographic light-sensitive material, and has heat sealability (heat seal strength). , Low-temperature heat-sealing property, hot-tack property, impurity-sealing property, heat-sealing strength after long-term aging, etc.). Further, it is possible to prevent rust and corrosion from occurring in the film forming machine.

Representative examples of the single-site catalyst include a metallocene catalyst comprising zirconocene dichloride and methylaminoxan having a uniform active site and discovered by Prof. Kaminsky of Germany. It has been announced. A typical example is disclosed in
0-35007, JP-A-60-35008, JP-A-60-35009, JP-A-3-207
703, JP-A-3-234711 and JP-A-4-300667.

The ethylene / α-olefin copolymer resin produced by polymerization using a metallocene catalyst has the following characteristics as compared with an ethylene / α-olefin copolymer resin produced by polymerization using a conventional Ziegler catalyst. i) It has 2-3 times the impact strength and tear strength. ii) Excellent transparency and gloss. iii) Excellent blocking resistance (less low-molecular-weight, low-density components called stickiness components). iv) Low melting point and excellent low temperature heat sealability. v) Excellent flexibility.

The polymerization method using the metallocene catalyst is as follows:
It is disclosed in numerous patent publications as exemplified below. JP-A-58-19309, JP-A-60-86
No. 2, JP-A-60-35006, JP-A-60-60
JP-A-350007, JP-A-60-35008,
JP-A-60-106008, JP-A-60-137
911, JP-A-61-31404, JP-A-61-108610, JP-A-61-221207
JP, JP-A-61-264010, JP-A-61-264010
-29609, JP-A-63-61010, JP-A-63-152608, JP-A-63-1
No. 78108, JP-A-63-222177,
JP-A-63-222178, JP-A-63-222
No. 179, JP-A-63-264606, JP-A-63-28070, and JP-A-63-501369.
Gazette, Japanese Patent Publication No. 64-6003, Japanese Patent Publication No. 64-4
No. 5406, JP-A-64-74202, JP-A-1-12407, JP-A-1-95110, JP-A-1-101315, JP-A-1-129
003, JP-A-1-207248, JP-A-1-210404, JP-A-1-251405, JP-A-1-259004, JP-A-1-275
609, JP-A-1-301704, JP-A-1-319489, JP-A-2-22307, JP-A-2-41303, JP-A-2-1731
No. 10, JP-A-2-302410, JP-A-3-302410
JP-A-56508, JP-A-3-62806, JP-A-3-66710, JP-A-3-70708, JP-A-3-70709, and JP-A-3-7071.
0, JP-A-3-74412, JP-A-4-8
704, JP-A-4-11604, JP-A-4-11604
-25514, JP-A-4-213305,
JP-A-5-310829, JP-A-5-32012
No. 2, JP-A-6-228222, JP-A-9-228
No. 40793, U.S. Pat. No. 4,522,982, U.S. Pat. No. 4,530,914 and the like.

Among the ethylene / α-olefin copolymer resins produced by polymerization using these metallocene catalysts, zirconium-based, hafnium-based, titanium-based, and vanadium-based copolymer resins having a small amount of catalyst residues that adversely affect the photographic properties of photographic light-sensitive materials. A highly active catalyst using at least one metallocene catalyst and capable of synthesizing a resin of 10,000 g or more per gram of the solid catalyst component is preferable. In particular, a metallocene catalyst comprising zirconocene dichloride and methylaluminoxane is preferred. The content of the residual halogen component which adversely affects the photographic properties in the resin is preferably 400 ppm or less, particularly preferably 15 ppm or less.
0 ppm or less is preferable. It is also possible to extract the catalyst residue using a catalyst deactivator in order to make the halogen content in the resin 400 ppm or less, or to provide a ventilator in a pelletizer or a film forming machine to reduce the residual halogen compound component. It is preferable for improving the rust prevention and photographic properties of the screws and dies of the extruder.

The most preferred polymerization method uses a metallocene catalyst at a polymerization temperature of 40 to 100 ° C. and a polymerization pressure of 5 to 50 kg.
Ethylene · alpha produced by gas phase polymerization method under the conditions of / cm ²
-An olefin random copolymer resin. Specifically, it is an ethylene / hexene-1 copolymer resin.

Specific examples of currently commercially available L-LDPE resins produced by polymerization using a metallocene-based catalyst, which is a typical example of a single-site catalyst, include: EXCEED (EXXon chemical) EXACT (EXXon chemical) AFFINITY (DOW chemical) ENGAGE (DOW chemical) LUFLEXENE (BASF) Evolu (Mitsui Petrochemical) Kernel (Mitsubishi Chemical) Yumerit (Ube Industries) Harmolex (Japanese polyolefin) Catalocene (Tosoh). As a polymerization method, a gas phase polymerization method is particularly preferable because it is inexpensive and has few residues that adversely affect photographic properties. A liquid phase polymerization method such as a suspension polymerization method or a solution polymerization method is also preferable from the viewpoint of ease of polymerization. Most preferred is a melt flow rate (ASTM D123) produced by a gas phase polymerization method.
Test temperature 190 ° C, test load 2.16 kg under E condition 8
f) is 0.1 to 20 g / 10 min, preferably 0.1 to 20 g / 10 min.
3 to 15 g / 10 min, more preferably 0.5 to 10 g / min
10 minutes, particularly preferably 0.8 to 7 g / 10 minutes, the density (A
STM D 1505) is 0.860-0.965 g / cm
³ , preferably 0.870 to 0.950 g / cm ³ , more preferably 0.880 to 0.940 g / cm ³ , and particularly preferably 0.890 to 0.930 g / cm ³ .

In order to prevent blocking and improve physical strength,
The molecular weight distribution (weight average molecular weight / number average molecular weight) determined by GPC is 5 or less, preferably 4 or less, particularly preferably 1.1 to 3, and most preferably 1.3 to 2.7.

The most preferred ethylene / α-olefin copolymer resin is an ethylene / α-olefin random copolymer resin. The composition of the ethylene / α-olefin copolymer resin is such that the α-olefin component is 1 to 9
9 mol%, preferably 1 to 95 mol%, more preferably 1 to 90 mol%, particularly preferably 2 to 80 mol%, most preferably 2 to 50 mol%, and the ethylene component is preferably 5 to 99 mol%. %, More preferably 10 to 99 mol%, particularly preferably 20 to 98 mol%, and most preferably 50 to 98 mol%. Representative examples of α-olefins include propylene, butene-1, hexene-1, pentene-1, 3-methyl-pentene-1, 4-methyl-pentene-1, octene-1, nonene-1, and decene-1. , Dodecene-1, tetracene-1, hexadecene-1, pentadecene-1, octadecene-1, heptene-1, eicosene-1, 4-methyl-hexene-1, 4,4-dimethylpentene-1 and the like Is one or two or more α-olefins of 3 to 20, preferably 4 to 15, particularly preferably 4 to 12, and most preferably 4 to 10.

The most preferred resin constituting the polyolefin resin film layer of the present invention is an ethylene / α-olefin random copolymer resin produced by polymerization using a metallocene catalyst. Specifically, it is an L-LDPE resin obtained by copolymerizing ethylene and hexene-1, which is an α-olefin having 6 carbon atoms, by a gas phase polymerization process. Any of these methods may be used as long as the polymerization is carried out in the presence of a metallocene catalyst.For example, polymerization in a high-pressure polymerization method is carried out at 120 ° C. in order to maintain the polymer in a solution state and to increase the polymerization activity. As described above, in order to suppress the chain transfer reaction that causes a decrease in the molecular weight and not to lower the polymerization activity, 3
At a temperature of 50 ° C or less, preferably 150 to 300 ° C, 4
00kg / cm ² or more, preferably carried out at a pressure of 500~2000kg / cm ^2. In addition, in the polymerization in the gas phase polymerization method, a high temperature is not preferable because the copolymer is in a powder state, and it is necessary that the temperature be 100 ° C. or lower. To increase the temperature, 50 ° C. or higher is preferable. In order to increase the polymerization activity, it is preferable to use a catalyst component preliminarily polymerized with an olefin, an organic aluminum compound and an ionized ionic compound. Further, in the polymerization in the solution polymerization method, the polymerization temperature needs to be 120 ° C. or more in consideration of the fact that the copolymer is in a solution state and that the polymerization activity is increased. The upper limit of the polymerization temperature is not particularly limited, but suppresses a chain transfer reaction that causes a decrease in molecular weight,
The temperature is preferably 300 ° C. or lower so as not to lower the catalyst efficiency. The pressure at the time of polymerization is not particularly limited, but is preferably at least atmospheric pressure and not more than 250 kg / cm ^{2 in} order to balance economy and polymerization activity.

In any case, the catalyst residue has an adverse effect on the photographic properties of the photographic light-sensitive material, and in addition, rust is generated on a resin contact portion of a mold or an extruder to deteriorate dimensional accuracy, and resin burning or spots are generated. Therefore, a smaller amount is preferable in the present invention.

Accordingly, in order to maintain good photographic properties, the amount of the residual halogen gas component in the packaging material for a photographic light-sensitive material of the present invention is 400 ppm or less, preferably 200 ppm or less, more preferably 100 ppm or less, particularly preferably 1 ppm or less. ８０80 ppm, most preferably 4-60 ppm.

The residual amount of any one of chromium, zirconium, titanium, hafnium and panadium is 200 p.
pm or less, preferably 200 ppm or less, more preferably 100 ppm or less, particularly preferably 60 ppm or less,
Most preferably, it is 40 ppm or less.

Particularly preferred ethylene / α in the present invention
-Olefin copolymer resin, ethylene in the presence of a catalyst containing a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton and optionally a cocatalyst, an organoaluminum compound, and a carrier. And 3 to 20 carbon atoms
Of α-olefins. Further, a catalyst obtained by pre-polymerizing ethylene and / or the α-olefin into the above catalyst may be used as the catalyst. Most preferred is ethylene-hexene-polymerized and produced by a low-pressure gas phase method using the above-mentioned polymerization catalyst.
1 is a random copolymer resin.

The cyclopentadienyl skeleton of the transition metal compound belonging to Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, which is a catalyst for producing the ethylene / α-olefin copolymer, is Pentadienyl group, substituted cyclopentadienyl group and the like. Examples of the substituted cyclopentadienyl group include a hydrocarbon group having 1 to 10 carbon atoms, a silyl group, a silyl-substituted alkyl group, a silyl-substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group,
And a substituted cyclopentadienyl group having at least one substituent selected from a halogen group, a haloalkyl group, a halosilyl group and the like. The substituted cyclopentadienyl group may have two or more substituents, and the substituents may combine with each other to form a ring.

The biodegradable polymer film layer and the biodegradable paper substrate may be laminated directly or via an adhesive layer. Further, the biodegradable polymer film layer and the thermoplastic resin film layer may be directly laminated or laminated via an adhesive layer. The biodegradable polymer film layer and the thermoplastic resin film layer, even if the biodegradable polymer film layer is on the photographic material side, so that the thermoplastic resin film layer is on the photographic material side Is also good.

As the adhesive layer, various known adhesive layers can be used according to the required characteristics. As an adhesive used for the adhesive layer, various polyethylenes (LDP)
E, L-LDPE, MDPE, HDPE) resins, polyolefinic thermoplastic resins such as various polypropylene resins, etc., ethylene-propylene copolymer resins, ethylene-vinyl acetate copolymer resins, ethylene-ethyl acrylate copolymer resins, etc. Hot melt adhesives (extrusion laminate adhesives) of special thermoplastic resins such as ethylene copolymer resins, ethylene-acrylic acid copolymer resins, ionomer resins, and acid-modified ethylene copolymer resins. In addition, there is a hot-melt type rubber-based adhesive, and as a solution adhesive, there is an adhesive for wet lamination, and an emulsion or latex adhesive. Representative examples of emulsion adhesives include polyvinyl acetate, vinyl acetate-
Emulsions include ethylene copolymers, vinyl acetate and acrylic ester copolymers, vinyl acetate and maleic ester copolymers, acrylic copolymers, and ethylene-acrylic acid copolymers. Representative examples of latex-type adhesives include rubber latex such as natural rubber, styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), and chloroprene rubber (CR). Further, as the adhesive layer of the present invention, heat-resistant, high peel strength, good easy-opening properties, and as a dry laminating adhesive capable of forming a layer thickness of 7 μm or less, two-part curing type, solvent type, There are non-solvent type, aqueous type, two-part solvent type, one-part non-solvent type, two-part non-solvent type, emulsion type, etc., acrylic adhesive, polyether adhesive, mixed adhesion of polyether and polyurethane. Adhesives, polyester- and polyurethane-based adhesives, polyester- and isocyanate-based adhesives, aromatic polyester-based adhesives, aliphatic polyester-based adhesives, aromatic polyether-based adhesives, aliphatic polyether-based adhesives Agents, polyester-based adhesives, isocyanate-based adhesives, urethane-based adhesives and the like.

The characteristics of the adhesive for dry lamination can be summarized as follows. Since the adhesive is used after being dissolved in a solvent, it can be used for various materials such as paper, thermoplastic resin film, non-woven fabric, synthetic paper, cellophane, etc., because it has good wettability to the substrate. A stable reaction and a strong adhesive force can be obtained, and the peel strength is 400 g / 1.
Good openability because it can be larger than 5mm width, good openability, excellent heat resistance, it is a reactive type, so it has a pot life (possible use time) after mixing with main material / curing agent and solvent, solid content coating amount 1 to 7 g / m ^2, preferably 2-5 g / m ² and can thin. However, aging is required at 30-65 ° C. for 1-5 days before complete curing.

Other hot-melt laminating blends of paraffin wax, microcrystalline wax, ethylene-vinyl acetate copolymer resin, ethylene / α-olefin copolymer resin, tackifier resin, ethylene-ethyl acrylate copolymer resin, etc. Known adhesives such as an adhesive, a pressure-sensitive adhesive, and a heat-sensitive adhesive can be used.

The polyolefin type adhesive for extrusion lamination, which is preferable as the adhesive layer of the present invention, is more specifically a homopolyethylene resin, a polypropylene resin, a polybutylene resin having various densities, and an ethylene copolymer (EVE, EEA, etc.). ) In addition to the resins, those obtained by copolymerizing ethylene with some other monomer (α-olefin) such as L-LDPE resin, ionomer resins such as “Surlyn” by Dupont and “Hyramin” by Mitsui Polychemicals (Ionic copolymers) and acid-modified polyolefin resins such as "Admer" of Mitsui Petrochemical Co., Ltd.
In addition, UV curable adhesives and the like have recently been used.

In particular, an LDPE resin, an L-LDPE resin, and a blend resin of an LDPE resin and an L-LDPE resin are preferred because they are inexpensive and have excellent laminating suitability. In order to improve the adhesive strength, an acid-modified polyolefin resin is preferred. Also, a mixed resin in which two or more of the above-mentioned resins are blended to cover the defects of each resin is particularly preferable because of its excellent laminating suitability. Especially LDPE resin or LL
In the present invention, it is particularly preferable to blend the DPE resin and the acid-modified polyolefin resin in an appropriate ratio, since the desired adhesive strength can be obtained. In order to improve the easy-openability by setting the interlayer peel strength of the laminated film to 350 g / 15 mm width or more, it is preferable that the dry laminating adhesive is a polyolefin type adhesive containing 5% by weight or more of an acid-modified polyolefin resin.

The acid-modified polyolefin resin refers to a modified polyolefin resin obtained by graft-modifying a polyolefin resin and an unsaturated carboxylic acid, such as a graft-modified polyethylene resin, a graft-modified polypropylene resin,
Graft-modified ethylene copolymer resin (EVA resin, EE
A resin, L-LDPE resin, EMA resin, etc.).

Graft modification with a polyolefin resin.
Unsaturated carboxylic acids are generic names including their derivatives. Typical examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, mesaconic acid, angelic acid, citraconic acid, crotone. Acid, isocrotonic acid, nadic acid, (endocis-
Bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate,
Ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, diethyl itaconate, Acrylamide, methacrylamide,
Maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutylamide, fumaric acid monoamide, fumaric acid Acid diamide, fumaric acid-N-monoethylamide, fumaric acid-N, N-diethylamide, fumaric acid-N
-Monobutylamide, fumaric acid-N, N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N,
N-dibutylamide, maleimide, monomethyl maleate, dimethyl maleate, potassium methacrylate, sodium acrylate, zinc acrylate, magnesium acrylate, calcium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, N-
Butylmaleimide, N-phenylmaleimide, maleenyl chloride, glycidyl maleate, dipropyl maleate,
Aconitic anhydride, sorbic acid and the like can be mentioned, and they can be mixed with each other. Among the acid-modified polyolefin resins, a maleic anhydride graft-modified polyethylene resin is preferred.

The method for graft-modifying unsaturated carboxylic acids in the modified polyolefin resin is not particularly limited. For example, the reaction is carried out in a molten state.
No. 21, JP-B-44-15422, which reacts in a solution state, a method disclosed in JP-B-43-18144, which reacts in a slurry state, and a gas phase. Tokubo 50-77
For example, there is a method disclosed in Japanese Patent No. 493 or the like.

Of these methods, the melt-kneading method using an extruder is preferred because it is simple in operation and inexpensive.

The amount of the unsaturated carboxylic acids used is determined based on the polyolefin resin base polymer (various polyethylene resins, various polypropylene resins, various polyolefin copolymer resins, polybutene-1 resin, poly-4
Α-olefin single resin such as -methylpentene-1 and copolymer resin thereof) 0.01 to 2 parts by weight per 100 parts by weight
0 parts by weight, preferably 0.2 to 5 parts by weight.

Representative examples of commercially available acid-modified polyolefin resins are shown below. (1) Nippon Petrochemical KK “N Polymer” (2) Mitsui Petrochemical KK “ADMER” (3) Showa Denko KK “ER RESIN” (4) Mitsubishi Kasei Kogyo KK “NOVATEC-AP” (5) Mitsubishi Yuka KK “MODIC” (6) Nippon Unicar KK “NUC-ACE” (7) Ube Industries KK “UBE BOND” (8) Tosoh KK “Lusen M” (9) Sumitomo Chemical KK “Bondyne” (10) Mitsui Dupont Chemical KK "CMPS" etc. (11) Exxon "Dexon" (12) Toa Fuels Industry KK "HA Series" (13) Mitsui Toatsu Chemicals KK "MITSULO LONPLY" etc.

The thickness of the extrusion-laminated adhesive layer is preferably from 7 μm to 50 μm, more preferably from 9 to 40 μm, and most preferably from 11 to 30 μm. Since it is determined based on the total thickness and the like, the numerical value is not particularly limited.

In recent years, non-solvent laminate adhesives that do not use solvents for pollution-sensitive adhesives have been spotlighted. This is a method in which a 100% solid urethane-based solventless adhesive is heated and applied to a substrate in a state where the viscosity is reduced, and another substrate is pressed and laminated with a heating roll. Since no solvent is used, there is no need for a dryer and no explosion-proof, exhaust, or ventilation equipment is required, but an adhesive heating device and a supply device are required. Since there is no solvent, there is no reaction suppression by the solvent, so the pot life is very short. Since the molecular weight of the adhesive is smaller than that of the solvent type, the cohesive strength is small and the initial adhesive strength is small. Although it has disadvantages such as requiring a long time to complete the reaction, it is particularly preferable because the photographic properties are good and there is no need to worry about residual solvent, and the coated amount of solid content is as small as 0.1 to 3.5 g / m ² .

The biodegradable polymer film layer, the thermoplastic resin film layer and the like may contain a light-shielding substance.

The light-shielding substance will be described. (1) Inorganic compound A. Oxide: 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, etc. 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. (2) Organic compounds Wood flour (pine, oak, sawdust, etc.), shell fiber ( Almonds, peanuts, fir shells, etc., cotton, jute, paper strips, non-wood fibers (straw, kenaf, bamboo, esparto, bagasse, moloheiya, smoke fire, etc.) cellophane pieces, nylon fibers, polypropylene fibers, starch (modified starch, Surface-treated starch), aromatic polyamide fibers, etc.

Among these light-shielding substances, inorganic compounds which do not adversely affect photographic properties and are stable to heat and opaque even at 150 ° C. or higher are preferable, and are particularly excellent in heat resistance and light resistance and relatively insensitive. The active materials black light absorbing carbon black, titanium nitride, graphite and iron black are preferred.

Examples of classification according to the raw material of carbon black include gas black, furnace black, channel black, anthracene black, acetylene black, Ketjen carbon black, thermal black,
There are lamp black, oil smoke, pine smoke, animal black, vegetable black and the like.

Representative examples of commercially available carbon black for coloring (including carbon black having improved conductivity) are, for example, carbon black # 20 (B) manufactured by Mitsubishi Kasei.
, # 30 (B), # 33 (B), # 40 (B), # 41
(B), # 44 (B), # 45 (B), # 50, # 55, # 1
00, # 600, # 950, # 1000, # 2200
(B), # 2400 (B), # 4000, # 4010, MA7,
MA8, MA11, MA100, MA100R, MA22
0, MA230, # as Mitsubishi conductive carbon black
3050, # 3150, # 3250, # 3600, # 3
750, # 3950 and the like.

Further, N110, N manufactured by Showa Cabot
134, N219, N220, N234, N326, N3
30, N330T, N339, N351, N550, M
AF, SRF and the like.

As overseas products, for example, Black Pearls L, 2, 46, 70, 71, 7 of Cabot Corporation
4,80,81,130,280,430,460,4
80,607,800,880,900,1000,11
00, 1300, 1400, etc., Regal 99, 25
0,300,330,400,415,660,99
1, SRF-S, Vulcan 3,6, P, XC-72
Etc., Sterling 10, SO, V, S, FT-F
F, MT-FF and the like.

Further, Unit of Ashland Chemical Co., Ltd.
ed R, BB, 15,102,3001,3004,30
06,3007,3008,3009,3011,301
2, XC-3016, XC-3017, 3020 and the like. In addition, Columbia Chemical Co.
nductex 975, SC, Raven C, H20, 4
10,420,430,450,460,500,52
0,760,790,850,890,1000,104
0,1060,1170,1190,1200,125
0,1255,2000,2500,3500,5000,5
250, 5750, 7000, and the like, but are not limited thereto.

A channel black produced by bringing a gas flame of natural gas or a gaseous or vaporous hydrocarbon into contact with the back surface of the channel steel while incompletely burning the gas flame in these various carbon blacks to precipitate the carbon black. Are not preferred in the present invention because they have high coloring power but poor photographic properties and pollute the air during production. The preferred carbon black in the present invention is acetylene black, natural gas, hydrocarbon oil or a mixture thereof.
Furnace black produced by continuous partial combustion in a furnace at 00 ° C to 1700 ° C or by thermal decomposition.

In the present invention, furnace carbon black is preferred for the purpose of improving light-shielding properties, cost, and physical properties. Examples of expensive light-shielding substances having an antistatic effect include various conductive carbon blacks and acetylene carbon blacks of various companies, Ketjen carbon black, which is a raw carbon black, is preferred. Particularly high sensitivity (ISO sensitivity 40
0 or more) 0.1% sulfur content for photographic materials
The following acetylene black and 1250 ° C to 1600 ° C
Furnace carbon black produced in the furnace described above is preferred.

The light-shielding substance having an antistatic effect has an average particle diameter of 12 to 50 μm and a DBP oil absorption of 100 ml /
100 g or more of various carbon blacks, various conductive carbon blacks, carbon fibers, metal fibers, Al-doped, Ti
O ₂ , SnO ₂ , metal-coated fiber, conductive material-containing fiber, metal powder, graphite, various metal salts, metal adsorption fiber, polyaniline, polypyrrole, polyacetylene, polydiacetylene, polyparaphenylene, graphite powder and the like. As for the antistatic agent, the various surfactants described above can be used. A particularly preferred light-shielding substance having an antistatic effect in the present invention is conductive carbon black.

Examples of the conductive carbon black include acetylene black, conductive furnace black (CF), superconductive furnace black (SCF), extra conductive furnace black (XCF), conductive channel black (CC), and a high temperature of about 1500 ° C. Furnace black or channel black heat-treated in the above. Specific examples of acetylene black include Denka acetylene black (manufactured by Denki Kagaku) and Shaunigan acetylene black (manufactured by Shaunigan Chemical Co., Ltd.). Specific examples of conductive furnace black include Continex CF (Continental Carbon Stocks). Company), Vulcan C (Cabot Corporation)
Examples of the superconductive furnace black include Continex SCF (manufactured by Continental Carbon Co., Ltd.) and Vulcan SC (manufactured by Cabot Corporation). Specific examples of the extra conductive furnace black include Asahi HS-500 (Asahi Carbon Co., Ltd.). Co., Ltd.), Vulcan XC-72 (Cabot Co., Ltd.)
Examples of the conductive channel black include Colux L (manufactured by Degussa Co., Ltd.), and commercially available conductive carbon blacks include:
Mitsubishi conductive carbon black (trade name: #
3050, # 3150, # 3250, # 3600, # 3
750, # 3950). Ketjen Black EC and Ketjen Black EC-600JD (Ketjen Black International Co., Ltd.), which are a kind of furnace black, can also be used. Among these, acetylene black is particularly excellent in conductivity because it has a low impurity content and has a developed secondary structure, and is particularly preferably used in the present invention. Further, Ketjen Black EC, Ketjen Black EC-600JD, and the like, which have excellent specific surface area and exhibit excellent conductivity even at a low filling amount, can be preferably used. The amount of the conductive carbon black to be added is 3 to 1 with respect to 100 parts by weight of the thermoplastic resin component.
00 parts by weight and 5 to 60 parts by weight are preferred, but especially 10 parts by weight.
It is preferably from 50 to 50 parts by weight, most preferably from 15 to 40 parts by weight. If the amount is less than 3 parts by weight, desired conductivity may not be obtained. If the amount exceeds 100 parts by weight, the physical strength, resin flowability and moldability of a film molded product may be reduced.

In order to impart conductivity to the light-shielding resin film layer of the present invention so that a static mark is not generated on a photographic light-sensitive material or to prevent a shock to a user, the conductive carbon is used. It is preferable that volume resistivity (measured at 20 ° C. and 60% RH) be 1 × 10 ² Ω · cm or less by containing black, and 1 × 1
It is more preferably 0 ¹⁰ Ω · cm or less, and 1 × 1
0 ⁷ Ω · cm or less is particularly preferable.
Most preferably, it is ⁶ Ω · cm or less. The volume resistivity (measured at 20 ° C. and 60% RH) is 1 × 10 ¹² Ω ·
If it exceeds cm, it is difficult to ensure sufficient antistatic properties, and static marks and the like are likely to be generated on the photographic material.

The volume specific resistance is a kind of electric resistance of a substance, and is an electric resistance inside the sample. That is, it is a value obtained by converting the volume resistance per unit volume, and
6911.

In a typical example, the MFR is 4.0.
g / 10 minutes, 20 wt% of an ethylene-hexene-1 random copolymer resin, which is an ultra-low density L-LDPE resin produced by a gas phase method using a metallocene catalyst having a density of 0.905 g / cm ³ , Crystallinity of 1 measured by X-ray diffraction
20% by weight of 5% ethylene-propylene copolymer resin
The MFR having a crystallinity of 67% (E condition of ASTM D1238) is 2.5 g / 10 min, and the density is 0.925 g / c.
41.8% by weight of m ³ low density homopolyethylene resin;
2% by weight of "Erest Master L / L-10" (trade name) manufactured by Kao KK, antistatic agent master batch, 0.1% by weight of calcium stearate as a lubricant, 0.05% by weight of bisfatty acid amide, as an antioxidant Hindered phenolic antioxidants (trade name “Irega” of Ciba Geigy)
Nox 1010 ") 0.05% by weight, 1% by weight of zeolite A which is a volatile gas (hydrogen cyanide, aldehyde, sulfur, etc.) adsorbing substance and an anti-blocking agent which adversely affects the photographic properties of the photographic light-sensitive material, and the following conductive property: A conductive polyolefin resin film having a thickness of 50 μm and comprising a resin composition containing 10% by weight of conductive carbon black.

When the following carbon black was used as the conductive carbon black at 15% by weight, the volume resistivity was as follows (except for the conductive carbon black, which was the same). Polyolefin resin film containing 10% by weight of Ketjen Black EC 7.6 × 10 ¹ Ω · cm Polyolefin resin film containing 10% by weight of Ketjen Black EC600JD 1.2 × 10 ¹ Ω · cm 10% by weight of acetylene black Polyolefin resin film containing 3.5 × 10 ⁵ Ω · cm Polyolefin resin film containing 10% by weight of Vulcan XC-72 2.8 × 10 ⁵ Ω · cm

This polyolefin resin film was excellent in conductivity, photographic properties, film moldability, heat sealing suitability and the like.

Instead of the low density homopolyethylene resin, high density homopolyethylene resin, ethylene / α-olefin copolymer resin, propylene / α-olefin copolymer resin, homopolypropylene resin, acid-modified polyolefin resin, ethylene / acrylic acid Copolymer resin, ethylene
Even when a polyolefin resin film containing at least one of ethyl acrylate copolymer resin, ethylene-methyl acrylate copolymer resin, and ethylene-vinyl acetate copolymer resin is used, a polyolefin resin film having substantially the same preferable properties is obtained. Obtained.

The volume resistivity (20 ° C., 60% R) of a film containing a high-density homopolyethylene resin as a main component
H) (measured in a constant temperature / humidity room).
For a film obtained by adding 10 parts by weight of Ketjen Black EC to 100 parts by weight of a high-density homopolyethylene resin having a density of 0.958 g / cm ³ , 2 × 10 ² Ω · cm,
6 × 10 Ω · cm for a film containing 10 parts by weight of Ketjen Black EC600JD, and 3.1 × 10 ⁶ Ω · c for a film containing 10 parts by weight of acetylene black.
m, and the film to which 10 parts by weight of Vulcan XC-72 was added had a value of 1.6 × 10 ⁶ Ω · cm. If necessary, it is also preferable to mix the former carbon black for coloring and the latter carbon black in an appropriate ratio according to the required characteristics.

In order not to adversely affect the photographic properties of the photographic light-sensitive material, the sulfur content in carbon black (according to ASTM D-1619 measurement method) should be 0.6.
The content is preferably not more than 0.3% by weight, particularly preferably not more than 0.3% by weight, most preferably not more than 0.1% by weight.

For this purpose, the selection of the raw material is important. For example, the above-mentioned sulfur content is as follows. Raw material Oil name Sulfur content in feed oil Creosote oil ｛Coal-based feedstock｝ 0.3-0.6% Ethylene bottom oil ｛Naphtha feedstock (petroleum-based feedstock)｝ 0.05-0.1% Ethylene bottom oil ｛ Gas oil feedstock (petroleum-based feedstock)｝ 0.2-1.5% Fluid catalytic cracking residue oil ｛petroleum-based feedstock｝ 0.2-4.0%

Therefore, as the raw material oil, ethylene bottom oil derived from creosote oil and petroleum is preferable, and ethylene bottom oil derived from naphtha having a sulfur content of 0.05 to 0.1% is produced as a raw material. Carbon black is
It is most preferable because the sulfur content in carbon black can be reduced to 0.1% by weight or less. As a production method, furnace carbon black produced in a furnace at 1200 ° C. to 1700 ° C., preferably 1250 ° C. to 1600 ° C. using the above raw materials is preferable. When carbon black produced using this ethylene bottom oil as a raw material is added to a biodegradable polymer film layer or a thermoplastic resin film layer, etc., it is added to ensure physical strength, heat sealing suitability, light shielding properties and antistatic properties. The amount is 0.1-60% by weight, 0.3
To 40% by weight is preferred, 0.5 to 20% by weight is more preferred, 1.0 to 20% by weight is particularly preferred, and 1.0 to 20% by weight is preferred.
10% by weight is most preferred.

In particular, free sulfur (free sulfur) which has been found to have a direct adverse effect on the photographic properties of photographic light-sensitive materials
hur) content (quantification according to JIS K 6350) is 100 ppm or less, preferably 50 ppm or less,
Particularly preferably 20 ppm or less, most preferably 10 p
pm or less of carbon black. In view of the fact that the free sulfur content is low, in the present invention, naphtha is used to produce ethylene bottom oil by continuous partial combustion in a furnace at 1250 ° C. to 1600 ° C. or by thermal decomposition. Furnace carbon black is most preferred.

Further, the carbon black was refluxed in the presence of sulfuric acid, and the generated hydrogen cyanide was trapped with a 0.1N aqueous sodium hydroxide solution, and then quantified by 4-pyridinecarboxylic acid / pyrazolone absorption spectrometry. In terms of% by weight based on the weight of carbon black 4
-The content of hydrogen cyanide by pyridine carboxylic acid / pyrazolone absorption spectrometry is preferably 0.01% by weight or less, particularly preferably 0.005% by weight or less, and most preferably 0.001% by weight or less. . Further, the content of the aldehyde compound by the iodine method is preferably 0.1% by weight or less, particularly preferably 0.05% by weight or less, and most preferably 0.01% by weight or less. Attention should be paid to the fact that even small amounts of these substances adversely affect the photographic properties of the photographic light-sensitive material.

Especially for photographic materials having high sensitivity (ISO sensitivity of 400 or more), acetylene black having a sulfur content of 0.1% or less, which has a good dispersibility and a large antistatic effect, is preferred. If necessary, acetylene black, furnace carbon black and Ketjen carbon black
It is also preferred to mix more than one species according to the required properties. The form in which the light-shielding substance is blended is roughly classified as follows. (1) Uniformly colored pellets (the most commonly used ones called color compounds) (2) Dispersible powders (treated with various surface treatment agents, also called dry colors, and a dispersing aid (3) Paste (dispersed plasticizer etc.) (4) Liquid (liquid dispersed in surfactant etc. also called liquid color) (5) ) Masterbatch pellets (light-shielding substance dispersed in plastic to be colored in high concentration) (6) Hygroscopic granular powder (dispersed light-shielding substance in plastic at high concentration (7) Dry powder (ordinary untreated dry powder)

There are various modes in which the light-shielding substance is mixed with the thermoplastic resin as described above, but the master batch method is preferable in terms of cost, prevention of workplace contamination, and the like. The present inventor has also disclosed in JP-A-63-186740 a colored masterbatch resin composition in which a light-shielding substance is dispersed in a specific ethylene / ethyl acrylate copolymer resin.

When used as a packaging material for a photographic light-sensitive material of the present invention, fog does not occur in the photographic light-sensitive material, and there is little occurrence of increase / decrease in sensitivity and large light-shielding ability.
Even in the case where it is added to the innermost layer (thermoplastic resin film layer), hardening of the carbon black (dust) and pinholes are less likely to occur in the film such as fish eye. The average particle size (measured by electron microscopy) is preferably from 6.0 to 9.0, particularly preferably from 10 to 80 mμ, and most preferably from 10 to 60 mμ. Among them, the volatile component (measured by JIS K 6221) is particularly 2.0% or less, and the DBP oil absorption (JIS K 6221).
Furnace carbon black having an oil absorption of 50 ml / 100 g or more and an ash content (JIS K6221) of 1.0% or less is inexpensive, has no adverse effect on photographic properties, and has an improved light-shielding property. It is preferable in terms of improved dispersibility and less decrease in physical properties. In particular, those obtained from ethylene bottom oil or creosote oil as the raw material oil are preferable, and those most preferable in the present invention are continuously produced in a furnace at 1250 ° C to 1600 ° C using ethylene bottom oil obtained from naphtha. Furnace carbon black having a DBP oil absorption of 70 ml / 100 g or more and an ash content of 0.5% or less produced by partial combustion or thermal decomposition.

Further, ASTM D 161 in the light-shielding substance is used.
The sulfur component according to the measurement method of 9-60 is 0.9% or less,
If the content is not preferably 0.7% or less, particularly preferably 0.5% or less, adverse effects on the photographic properties of the photographic material, such as an increase in fog, abnormal sensitivity, and abnormal occurrence. In particular, a free sulfur component which greatly adversely affects the photographic properties of the direct photographic light-sensitive material (each sample is cooled and solidified with liquid nitrogen, then pulverized, and 100 g of the pulverized sample is placed in a Soxhlet extractor, extracted with chloroform at 60 ° C. for 8 hours, and cooled. 10 ml of this solution was injected into a high-performance liquid chromatograph to determine the amount of sulfur, and the high-performance liquid chromatographic separation conditions were as follows: column: ODS silica column (4.6 φ × 150 m)
m), separation solution; methanol 95 and water 5 (containing 0.1% of acetic acid and triethylamine each), flow rate: 1 ml /
Min, detection wavelength: 254 nm, quantification is performed by the absolute calibration curve method. ) Is less than 0.1%, preferably less than 0.05%,
Particularly preferably 0.01% or less, most preferably 0.0% or less.
Not more than 05%. Although expensive, acetylene black having a sulfur content of 0.1% or less has an ISO sensitivity of 100.
The above photographic materials are suitable for maintaining good photographic properties.

The content of the light-shielding substance in the biodegradable polymer film layer and / or the thermoplastic resin film layer is 0.1.
To 60% by weight, preferably 0.3 to 40% by weight,
-20% by weight is more preferable, 1.0-20% by weight is particularly preferable, and 1.0-10% by weight is most preferable.

The above biodegradable polymer film layer and / or thermoplastic resin film layer can be provided with a metal or inorganic compound vapor-deposited film. As the metal deposited film, there is an aluminum deposited film, and as the deposited film of the inorganic compound,
Silicon oxide, aluminum oxide, titanium oxide, tin oxide,
There are vapor-deposited films of zinc oxide, isodium oxide, magnesium oxide, and the like.

The thickness of the deposited film is 50-3,000.
Is preferably 100 to 2,500 °, and most preferably 200 to 2,000 °. If the thickness is less than 50 mm, the moisture-proof property and oxygen barrier property may not be sufficiently secured. If the thickness exceeds 3,000 mm, thermal degradation of the biodegradable polymer film layer or the thermoplastic resin film may occur. Thermal deformation increases,
Not only the physical strength and appearance are deteriorated, but also the productivity is reduced and the cost is increased. Deposition film processing Water vapor transmission rate of a biodegradable polymer film layer or a thermoplastic resin film (JIS Z020
8 Conditions B) of preferably less 10 g / m ² · 24 hours · 1 atm, more preferably from 7 g / m ² · 24 hours · 1 atm or less, 5 g / m ² · 24 hours · 1 atm or less is particularly preferred Most preferred is 3 g / m ² · 24 hours · 1 atm. If the water vapor transmission rate exceeds 10 g / m ² · 24 hours · 1 atm, the photographic properties of the packaged photographic light-sensitive material are adversely affected.

Further, the oxygen permeability (JIS K7) of the deposited biodegradable polymer film layer and the thermoplastic resin film is processed.
126) is preferably less 50 cc / m ² · 24 hours · 1 atm, more preferably not more than 40 cc / m ² · 24 hours · 1 atm or less, and most preferably 30 cc / m ² · 24 hours · 1 atm. If the oxygen permeability exceeds 50 cc / m ² · 24 hours · 1 atm, the photographic properties of the packaged photographic material are adversely affected.

The application to which the packaging material for photographic light-sensitive material of the present invention can be applied will be described.

(1) A moisture-proof / sealing packaging bag for packaging a transparent, colored or printed film unit with a lens (Japanese Patent Publication No.
1380, JP-A-5-1970087, JP-A-7-72593, JP-A-8-248573, JP-A-8-254793, JP-A-8-334
869, JP-A-9-15796, JP-A-9
-54395, JP-A-9-120119,
JP-A-9-244187, JP-A-9-27428
No. 8, JP-A-10-186586, JP-A-10-186586
0-197994).

(2) A moisture-proof / sealing packaging bag (Japanese Unexamined Patent Application Publication No. H8 (1996)) which collectively packages two or more photographic films for photography (JIS 135 film, APS film, microfilm, etc.) in a transparent, colored or printed plastic container. -254
793).

(3) Moisture-proof / sealing / light-shielding bags for sheet-like photographic materials such as photographic paper, film for printing plate making, cut film for photographing, X-ray film, PS plate, etc.
2700, JP-A-8-254793, JP-A-5-5972, etc.).

(4) Light-shielding film for a band-shaped photographic photosensitive material package (JP-A-2-72347, JP-A-6-21)
No. 4350, Japanese Utility Model Publication No. 5-29471, Japanese Utility Model Publication No. 6-8593, Japanese Utility Model Publication No. 7-50743, Japanese Utility Model Publication No. 8-10812, Japanese Utility Model Publication No. 63-153255.
No.).

(5) Moisture-proof sealed light-shielding bags for roll-shaped photographic light-sensitive materials such as photographic paper, movie films, micropositive films, printing plate-making films, and thermally developed diffusion transfer paper
-67358, etc.).

(6) Moisture-proof / light-shielding film or leader film for light-room-packed packaging of strip-shaped photosensitive material such as photographic paper or photographic film (Japanese Patent Application Laid-Open Nos. 62-172344, 2-72347, 5-72672,
JP-A-5-216176, JP-A-6-75341
JP-A-6-214350, JP-A-6-214350
48820, JP-A-7-257510, JP-A-7-92618, JP-A-8-40468, JP-A-10-97036, and JP-B-56-16.
No. 608, Japanese Utility Model Publication No. 6-8593, Japanese Utility Model Publication No. 8-
No. 9725).

(7) A moisture-proof and light-shielding film for packaging a bulk roll-shaped photographic light-sensitive material (JP-A-3-53243).

(8) Instant film pack (JP-A-8-62782, JP-A-10-228079, JP-A-10-228080, etc.).

(9) A light-shielding bag for an instant film pack or the like in which a plurality of self-developing film units are stacked and light-tightly housed in a light-shielding bag (Japanese Patent Laid-Open No. 8-62782).
JP, JP-A-10-186504, JP-A-10-186504
-221814, JP-A-10-22879, JP-A-10-228080, JP-A-10-2
No. 88810, JP-A-10-293359,
JP-A-10-301199, JP-A-10-301
248, etc.).

(10) Light-shielding paper for photographic films (US Pat. No. 5,790,912, JP-A-48-22020, JP-A-50-67644, JP-A-52-1)
No. 50016, JP-A-55-140835,
JP-A-58-17434, JP-A-58-1867
44, JP-A-59-68238, JP-A-6
0-35728, JP-A-61-36216, JP-A-63-169624, JP-A-4-13.
6842, JP-A-4-296849, JP-A-5-281666, JP-A-9-80695, JP-A-9-152885, JP-A-9-185
151, JP-A-10-104803, JP-A-10-254102, JP-A-10-25410
No. 3, JP-A-10-312042, JP-A-10-312042
0-312043, JP-A-10-319545, JP-A-10-325993, etc.).

The above-mentioned various sealing bags include a bottom sealing bag of a tubular film, a two-side sealing bag, a three-side sealing bag, a four-side sealing bag, a gusset bag and the like.

Further, it can be used for various overwrapping packages. For example, there are carton or tray overwrapping, caramel overwrapping, snack overwrapping, cigarette overwrapping, roll overwrapping, bar overwrapping, twist overwrapping, and the like. Further, it can be used as various packaging bodies described in the Japan Packaging Technology Association, published on July 1, 1995, Handbook of Packaging Technology, pages 754 to 774.

The photographic light-sensitive materials to which the packaging material for photographic light-sensitive materials of the present invention can be applied are shown below. (1) Silver halide photographic materials (film for printing, color or black and white photographic paper, color or black and white negative film, master paper for printing, DTR (diffusion transfer) photosensitive material,
Computerized typesetting film and paper, color or black-and-white positive film, color reversal film, microfilm, surveillance film, movie film, self-developing photographic light-sensitive material, direct positive film and paper, etc.) Developed color light-sensitive materials, heat-developable black-and-white light-sensitive materials (for example, JP-B-43-4921 and JP-B-43-4924, pages 553 to 555 of "Basics of photographic engineering", silver halide photography, published by Corona Co., 1879). And Research Tis Closure Magazine, June 1978, 9
Pages 15 to 15 (RD-17029). Further, JP-A-59-12431 and JP-A-60-124
Nos. 2950 and 61-52343 and U.S. Pat. No. 4,584,267). (3) Photosensitive and heat-sensitive recording materials Recording material using photothermography (photosensitive / thermal image forming method) described in JP-A-3-72358) (4) Diazonium photographic photosensitive material (4-morpholinobenzenediazonium microfilm, microfilm, for copying) (5) Azide and diazide photographic photosensitive materials (photosensitive materials containing para-azide benzoate, 4,4'diazidostilbene, etc., such as copying films and printing plate materials) (6) ) Quinonediazide-based photographic materials (orthoquinonediazide, orthonaphthoquinonediazide compounds such as benzoquinone (1,2)- Photosensitive material containing diazide- (2) -4-sulfonic acid phenyl ether, etc., for example, printing plate material, copying film, adhesive film, etc. (7) Photopolymer (photosensitive material containing vinyl monomer, etc.) (8) Polyvinylcinnamate-based photosensitive materials (eg, printing films, resists for ICs, etc.)

The layer structure of the packaging material for a photographic light-sensitive material of the present invention will be described with reference to the drawings.

The packaging material for photographic light-sensitive material shown in FIG. 1 has a biodegradable paper substrate 1 and a light-shielding material from the outer side (the outer side of the package when wrapping the photographic light-sensitive material, the upper side in the figure). The biodegradable polymer film layer 2 containing no substance is directly laminated.

The packaging material for photographic light-sensitive material shown in FIG. 2 has a biodegradable paper base material 1 and a biodegradable polymer film layer 2a containing a light-shielding substance directly laminated from the outer surface side. is there.

In the packaging material for photographic light-sensitive material shown in FIG. 3, a biodegradable paper base material 1a containing a light-shielding substance and a biodegradable polymer film layer 2a containing a light-shielding substance are directly contacted from the outer surface side. They are stacked.

The packaging material for photographic light-sensitive material shown in FIG. 4 has a biodegradable paper substrate 1a containing a light-shielding substance from the outer side.
And a biodegradable polymer film layer 2 containing no light-shielding substance, which is laminated via an adhesive layer 3.

The packaging material for photographic light-sensitive material shown in FIG. 5 has a biodegradable paper base material 1 containing no light-shielding substance and a biodegradable polymer film layer 2a containing a light-shielding substance, from the outer side. Are laminated with the adhesive layer 3 interposed therebetween.

The packaging material for photographic light-sensitive material shown in FIG. 6 has a two-layer co-extruded film layer in which two biodegradable polymer film layers 2 containing no light-shielding substance are laminated from the outer surface side.
II.

The packaging material for photographic light-sensitive material shown in FIG. 7 has a two-layer coextruded film layer IIa in which two biodegradable polymer film layers 2a containing a light-shielding substance are laminated from the outer surface side.
It consists of

The packaging material for a photographic light-sensitive material shown in FIG. 8 has a thermoplastic resin film layer 4 containing no light-shielding substance and a biodegradable polymer film layer containing no light-shielding substance, from the outer side. No. 2 comprising a two-layer coextruded film layer II.

The packaging material for photographic light-sensitive material shown in FIG. 9 comprises, from the outer side, a thermoplastic resin film layer 4a containing a light-shielding substance and a biodegradable polymer film layer 2a containing a light-shielding substance. It consists of a layer coextruded film layer IIa.

The packaging material for photographic light-sensitive material shown in FIG.
It consists of a two-layer co-extruded film layer IIa of a biodegradable polymer film layer 2a containing a light-shielding substance and a thermoplastic resin film layer 4a containing a light-shielding substance from the outer side.

The packaging material for photographic light-sensitive material shown in FIG.
A vapor-deposited film-processed biodegradable biopolymer film layer 5 obtained by processing the vapor-deposited film M on a biodegradable biopolymer film layer 2 containing no light-shielding substance, and a biodegradation containing no light-shielding substance from the outer surface side. The raw polymer film layer 2 is laminated via the adhesive layer 3.

The packaging material for a photographic light-sensitive material shown in FIG.
A vapor-deposited film-processed biodegradable biopolymer film layer 5a obtained by processing a vapor-deposited film M on a biodegradable biopolymer film layer 2a containing a light-shielding substance, and a biodegradable biopolymer film containing a light-shielding substance The layer 2 a is laminated via the adhesive layer 3.

The packaging material for photographic light-sensitive material shown in FIG.
A vapor-deposited film-processed biodegradable biopolymer film layer 5 obtained by processing a vapor-deposited film M on a biodegradable biopolymer film layer 2 containing no light-shielding substance, and a biodegradable biomass containing light-shielding substance from the outer surface. Two-layer coextruded film layer IIa of molecular film layer 2a and thermoplastic resin film layer 4a containing a light-shielding substance
Are laminated with the adhesive layer 3 interposed therebetween.

The packaging material for a photographic light-sensitive material shown in FIG.
From the outer side, a two-layer co-extruded film of a biodegradable biopolymer film layer 2, a biodegradable biopolymer film layer 2a containing a light-shielding substance, and a thermoplastic resin film layer 4 not containing a light-shielding substance The layer IIa is laminated via the adhesive layer 3.

[0147]

EXAMPLES Example 1 A packaging material for a photographic photosensitive material having a layer structure corresponding to FIG.

<Biodegradable paper substrate 1> Non-wood pulp, a kind of natural pulp, having a thickness of 50 using kenaf bast fiber
μm unbleached paper.

<Biodegradable polymer film layer 2a> 50 parts by weight of a biodegradable aliphatic polyester resin composed of a copolymer of polylactic acid and polycaprolactone, MFR (ASTM
D 1238 E condition) was 5 g / 10 min, and the density (AST
MD 1505) of 0.915 g / cm ³ , Shore hardness (D scale of ASTM D 2240) of 53D, Vicat softening point (ASTM D 1525) of 97 ° C, melting point (ASTM D 2117) of 111 ° C, and metallocene catalyst. Hexene polymerized by gas phase method
1 20 parts by weight of copolymer resin, 20 parts by weight of calcium carbonate, adsorption amount of 105 mg / g, DBP oil absorption of 1
Resin composition of 25 cc / 100 g, pH 7.5, acetone extractables 0.05%, volatiles 0.2%, ash content 0.06%, and 10 parts by weight of acetylene carbon black having an average particle diameter of 40 mμ It is a light-shielding film having a thickness of 80 μm.

<Adhesive Layer> A two-component polyurethane-type dry laminate adhesive layer having a thickness of 3 μm (90% by weight of A-310, a main agent manufactured by Takeda Chemicals, and 10% by weight of A-3, a hardener). Adhesive).

In these, the above-mentioned adhesive layer is formed at a rate of 100 m / min by a dry laminating method to adhere the biodegradable paper base material to the biodegradable polymer film layer.
Aging was performed for 5 days. Moisture permeability (JIS Z 02
08, the condition B) is 4 g / m ² · 24 hours and the total thickness is 1
33 μm.

The packaging material for a photographic light-sensitive material is entirely composed of a biodegradable polymer, has microbial degradability, and has a light-shielding property, heat-sealing suitability, photographic property, antistatic property, physical strength and other photographic properties. It satisfies the characteristics required for packaging materials for photosensitive materials. In addition, since a biodegradable polymer film layer containing a large amount of calcium carbonate is used, it has excellent physical strength and can reduce the amount of heat generated by incineration, etc. The needs are also satisfactory. Further, the packaging bag made by using this packaging material for photographic light-sensitive materials was able to secure long-term (one year or more) sealing and complete light-shielding properties.

Example 2 A packaging material for a photographic photosensitive material having a layer structure corresponding to FIG. The biodegradable paper substrate 1 and the biodegradable biopolymer film layer 2a are the same as in Example 1.

The adhesive layer 3 was composed of 20 parts by weight of an acid-modified polyolefin resin (manufactured by Mitsubishi Yuka, MODIC) and a melt index (E condition of ASTM D1238) of 5.1 g /
10 minutes, density (ASTM D 1505) 0.917 g /
cm ³ , Shore hardness (D scale of ASTM D2240) 46D, Vicat softening point (ASTM D152
5) comprises a polyolefin resin composition comprising 80 parts by weight of a low-density homopolyethylene resin at 82 ° C.
5 μm.

In these methods, the adhesive layer was heated at a resin temperature of 34.
Extrusion lamination was performed at 5 ° C. and a laminating speed of 150 m / min to bond the biodegradable paper substrate and the biodegradable polymer film layer. The moisture permeability (condition B of JIS Z 0208) is 3 g / m ² · 24 hours, and the total thickness is 145 μm.
m.

The packaging material for photographic light-sensitive material of Example 2 has a laminating speed 50% (100 → 150 m / min) faster than the packaging material for photographic light-sensitive material of Example 1, and does not require an aging step, and is inexpensive. , Moisture resistance and physical strength were also excellent. (130 μm / 145 μm) × 10 in thickness ratio
Since 0 (%) = 89.7% is made of a biodegradable polymer, it is also excellent in biodegradability, does not generate harmful gas upon incineration, and has other properties as in Example 1. Was.

Example 3 This is a packaging material for a photographic photosensitive material having a layer structure corresponding to FIG. The biodegradable polymer film layer 2a on the inner surface side (the inner side of the package when the photographic photosensitive material is wrapped, the lower side in the figure) is made of the same resin composition as in Example 1, and is black and thick. The height is 50 μm.

The biodegradable polymer film layer 2a on the outer side (the outer side of the package when the photographic photosensitive material is wrapped, the upper side in the figure) is composed of 10 parts by weight of corn starch instead of 10 parts by weight of acetylene carbon black. Is composed of the same resin composition as that constituting the biodegradable polymer film layer 2a of Example 1 except that
0 μm.

These biodegradable polymer film layers 2a,
2a is manufactured by a two-layer coextrusion film forming method. The moisture permeability (condition B of JIS Z 0208) is as follows:
7 g / m ² · 24 hours, total thickness was 100 μm.

The packaging material for a photographic light-sensitive material was prepared in Example 1.
And 2, compared to the packaging materials for photographic light-sensitive materials,
It was one of the most preferable packaging materials for photographic light-sensitive materials, which had further excellent physical strength, was inexpensive, and had excellent heat resistance, appearance, light shielding properties, dust resistance and smoothness.

Example 4 A packaging material for a photographic photosensitive material having a layer structure corresponding to FIG. The biodegradable polymer film layer 2a is made of the same resin composition as the black biodegradable polymer film layer 2a of Example 1, and has a thickness of 90 μm.

[0162] The thermoplastic resin film layer 4a
From 90 parts by weight of an ethylene-hexene-1 copolymer resin produced by a gas phase method using a metallocene catalyst, which is one of the components constituting the biodegradable polymer film layer 2a, and 10 parts by weight of acetylene carbon black. Is a film layer having a thickness of 10 μm and having no biodegradability.

The biodegradable polymer film layer 2a and the thermoplastic resin film layer 4a are manufactured by a two-layer co-extrusion film forming method. Since the ratio of the biodegradable polymer film layer 2a to the entire thickness is 90%, the biodegradable polymer film layer 2a has excellent biodegradability and does not generate harmful gas when incinerated. The moisture permeability (condition B of JIS Z 0208) was 2.6 g / m ² · 24 hours.

The packaging material for a photographic light-sensitive material was prepared in Example 3.
Heat sealability, physical strength, and film formability were more excellent.

Example 5 Instead of 50 parts by weight of the biodegradable aliphatic polyester resin comprising the copolymer of polylactic acid and polypropylene of Example 1, the biodegradability comprising a copolymer of polylactic acid and polycaprolactone was used. A packaging material having the same configuration as in Example 1 was used except that 50 parts by weight of the aliphatic polyester resin was used. The characteristics were substantially the same as those in Example 1.

[0166]

Since the present invention is configured as described above, it has the following effects. (1) It has various physical strengths and moisture proofness essential for packaging materials for photographic photosensitive materials, and has microbial degradability. (2) Disposal and incineration of packaging materials for photographic light-sensitive materials does not adversely affect living organisms and plants. (3) Photographic properties that are necessary for packaging materials for photographic photosensitive materials without using metal foils that are expensive, cannot be incinerated, reduce physical strength, and adversely affect photographic properties due to thermal decomposition of rolling oil. In addition, a packaging material having excellent physical characteristics can be provided at low cost. (4) The use of a polymer that can reduce CO ₂ gas, which causes global warming, can prevent the global environment from deteriorating.
Clear the Containers and Packaging Recycling Law, which will be enforced from April 2000.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view showing a layer structure of an embodiment of a packaging material for a photographic photosensitive material according to the present invention.

FIG. 2 is a partial cross-sectional view showing a layer configuration of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 3 is a partial cross-sectional view showing a layer configuration of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 4 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 5 is a partial cross-sectional view showing a layer configuration of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 6 is a partial cross-sectional view showing a layer structure of one embodiment of a packaging material for a photographic light-sensitive material according to the present invention.

FIG. 7 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 8 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photosensitive material according to the present invention.

FIG. 9 is a partial cross-sectional view showing a layer configuration of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 10 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 11 is a partial cross-sectional view showing a layer configuration of an embodiment of a packaging material for a photographic light-sensitive material according to the present invention.

FIG. 12 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 13 is a partial cross-sectional view showing a layer structure of another embodiment of the packaging material for a photographic light-sensitive material according to the present invention.

FIG. 14 is a partial cross-sectional view showing the layer structure of another embodiment of the packaging material for a photosensitive material according to the present invention.

[Explanation of symbols]

 1, 1a: biodegradable paper substrate 2, 2a: biodegradable polymer film layer 3: adhesive layer 4, 4a: thermoplastic resin film layer M: vapor deposited film II, IIa: multilayer co-extruded film a: light shielding Show that

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI theme coat ゛ (reference) C08J 5/18 C08J 5/18 F term (reference) 4F071 AA02 AA09 AA15 AA73 AA74 AF10 AF10Y AF59 AH04 BB06 BC01 BC12 4F100 AA08A AA37A AJ04B AK01A AK01B AK04B AK41A AK51B AL01B BA02 CA02 CB03 DG10B EH20 GB27 JB16B JC00A JC00B JD04 JK01 JL00 JL12B JN02A YY00 YY00B

Claims (5)

[Claims] 1. A film comprising two or more layers, at least one of which is a biodegradable polymer film layer having a moisture permeability (condition B of JIS Z 0208) of 10 g / m ² · 2.
A wrapping material for a photographic light-sensitive material, wherein the wrapping time is 4 hours or less. 2. A biodegradable paper base made of natural pulp or biodegradable polymer pulp, wherein a layer other than the biodegradable polymer film layer among the two or more layers is formed. 2. The packaging material for a photographic light-sensitive material according to 1. 3. The packaging material for a photographic light-sensitive material according to claim 1, wherein the biodegradable polymer film layer is formed in a thickness ratio of 70% or more. 4. A layer other than the biodegradable polymer film layer among the two or more layers is a biodegradable polymer film layer, and the two biodegradable polymer film layers are co-extruded. The packaging material for a photographic photosensitive material according to claim 1, which is formed. 5. A thermoplastic resin film layer in which, of the two or more layers, a layer other than the biodegradable polymer film layer contains 5% by weight or more of an ethylene copolymer resin and has heat sealability. The packaging material for a photographic light-sensitive material according to claim 1, which is: