JP2000066336A - Molding for photographic sensitive material and photographic sensitive material package using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding for a photographic sensitive material good in anti-bleed-out characteristic, photographic performances, print image quality or the like, excellent in physical strength(especially, at a low temp.), good in formability and excellent in the dispersibility of recycled resins, dyes, pigments or the like even in the case of containing one or more of antioxidants, lubricants and surfactants which deteriorate the photographic properties or the print image quality. SOLUTION: A light shielding film for a photographic sensitive material is formed by a single layer film composed only of a light shieldable thermoplastic resin film layer 1a. The light shieldable thermoplastic resin film layer 1a is formed by using a resin composition produced by compounding 0.001-20 parts by weight of at least one of lubricants, surfactants and antioxidants and 0.1-150 parts by weight of at least one plasticizer per 10 parts by weight of the total content of the thermoplastic resin (provided that, except vinyl chloride resins, vinylidene chloride resins and chlorinated polyolefin resins).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article for a photographic light-sensitive material which has improved moldability, physical strength, appearance (aesthetic appearance, etc.) without adversely affecting the photographic properties of the photographic light-sensitive material, and uses the same. It relates to a photographic photosensitive material package.

[0002]

2. Description of the Related Art Conventionally, resins having various resin compositions have been proposed as resins used for molded articles for photographic photosensitive materials such as light-shielding laminated films and photographic film cartridges used for packaging bags of photographic photosensitive materials. For example, Tokuhei 2-27
No. 00 proposes a photosensitive material packaging film formed of a resin composition comprising 50% by weight or more of an ethylene / α-olefin copolymer resin and 1% by weight or more of a light-shielding substance.

[0003] Japanese Patent Publication No. 2-38939 proposes a photographic film container formed of a resin composition containing 70% by weight or more of a polypropylene resin having special physical properties.

Japanese Patent Application Laid-Open No. 62-284355 discloses that 0.05 to 3% by weight of carbon black, 0.2 to 2% by weight of carboxyl-modified silicone oil and 0.5% by weight of rubber are used.
2. Description of the Related Art A photographic film spool mainly comprising a rubber-containing polystyrene resin (generally referred to as a high-impact polystyrene resin) of an amorphous resin containing up to 6% by weight has been proposed.

[0005] Japanese Utility Model Publication No. 5-2919 discloses that a photographic film (including an APS patrone of a resin patrone recently released in addition to a conventional metal patrone) is provided in advance in a unit body having a photographing function. A film unit with a lens has been proposed in which the main unit is mainly composed of carbon black and rubber-containing polystyrene resin.

[0006]

However, the resin compositions used in the above-mentioned conventional molded articles for photographic light-sensitive materials each have problems. That is, Tokuhei 2
No. 2700 proposes that the film formability and the dispersibility of the light-shielding substance are not sufficient, and it is desired that the appearance be further improved.

The one proposed in Japanese Patent Publication No. 2-38939 is very excellent in appearance and injection moldability, but has low physical strength at low temperature and further improves bleed-out of additives. Was desired. Furthermore, since the main component is a crystalline resin of a polypropylene resin, improvement in dimensional accuracy has been strongly desired.

The one proposed in Japanese Patent Application Laid-Open No. 62-284355 has insufficient physical strength, high water absorption,
Bleed-outs such as silicone oils are common, and it has been desired to improve these drawbacks.

The one proposed in Japanese Utility Model Publication No. 5-2919 has a rubber-containing polystyrene resin as a main component, and therefore, it has been strongly desired to improve photographic properties, moldability and dimensional accuracy.

An object of the present invention is to provide a molded article for photographic light-sensitive materials in which various disadvantages are further improved while maintaining the excellent characteristics of the above-mentioned conventional resin composition while further improving the defects.

That is, even when the photosensitive material contains one or more of an antioxidant, a lubricant, and a surfactant which are liable to bleed out and deteriorate photographic properties and print quality, the bleed-out resistance is improved. A molded article for a photographic photosensitive material having excellent photographic properties, print quality, etc., excellent physical strength (especially at a low temperature), good moldability, and excellent dispersibility of recycled resin and dye / pigment. An object of the present invention is to provide a photographic photosensitive material package.

[0012]

Means for Solving the Problems The molded article for photographic light-sensitive material of the present invention is based on 100 parts by weight of the total content of thermoplastic resin (excluding vinyl chloride resin, vinylidene chloride resin and chlorinated polyolefin resin). Resin comprising a total content of at least one of a lubricant, a surfactant and an antioxidant of 0.001 to 20 parts by weight, and a content of at least one of a plasticizer and 0.1 to 150 parts by weight. It is characterized by being molded using the composition.

In the molded article for photographic light-sensitive material of the present invention, by combining one or more of a lubricant, a surfactant and an antioxidant with a plasticizer, photographic properties, bleed-out resistance and physical properties are improved. It improves strength, moldability, and dispersibility of light-shielding substances such as recycled resins and dyes and pigments.

The photographic light-sensitive material package of the present invention comprises a photographic light-sensitive material, a molded article for the photographic light-sensitive material to which the photographic light-sensitive material is applied, and JIS Z 0208 in which the molded article for the photographic light-sensitive material is hermetically packaged. And a moisture-proof packaging material having a moisture permeability of 10 g / m ² · 24 hours or less according to the condition B measurement method.

In the photographic light-sensitive material package of the present invention,
As described above, the physical strength and moldability of the molded article for photographic light-sensitive materials, the dispersibility of light-shielding substances such as recycled resins and dyes and pigments are improved, and the moisture-proof packaging material transfers moisture to the molded article for photographic light-sensitive materials. To prevent the photographic properties of the photographic material from deteriorating.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition used for the molded article for photographic light-sensitive materials of the present invention is composed of a thermoplastic resin (however, excluding vinyl chloride resin, vinylidene chloride resin and chlorinated polyolefin resin). .

This thermoplastic resin can be applied to the present invention singly or as a blend of two or more kinds at an arbitrary ratio. Specific examples include various polyolefin resins, aromatic vinyl resins, polystyrene resins, polyphenylene ether resins, polyphenylene sulfide resins, polyacrylate resins, copolymers of styrene and synthetic rubber, polystyrene resins and synthetic rubber ( (Including thermoplastic elastomers), acrylonitrile / butadiene / styrene terpolymer resin, polyamide resin, polyester resin, polyester liquid crystal resin, polyacetal resin, polycarbonate resin, partially saponified polyvinyl acetate resin, polyethylene Examples include naphthalate resin, polyethylene terephthalate resin, polybutene terephthalate resin, modified polyphenylene oxide resin, polyacrylonitrile resin, and the like.

Among these thermoplastic resins, polystyrene resins and polyolefin resins which are inexpensive with little adverse effect on photographic properties, are available worldwide, and have sufficient physical strength for use in the present invention can be used. Is particularly preferred. The polystyrene resin is a syndiotactic polystyrene resin produced by polymerization using a known rubber-modified styrene resin and a metallocene catalyst.

The thermoplastic resin is suitably a polyolefin resin at 50% by weight or more, preferably at least 70% by weight, more preferably at least 80% by weight, particularly preferably at least 90% by weight, most preferably at least 90% by weight. Preferably 1
00% by weight.

Polyolefin resins include homopolyethylene resin, ultrahigh molecular weight polyethylene resin, cyclic polyethylene resin, random or block copolymer resin of ethylene and α-olefin, homopolypropylene resin, random or block of propylene and α-olefin. There are copolymer resins, acid-modified polyolefin resins, ethylene-acrylate copolymer resins, ethylene-vinyl acetate copolymer resins, and the like. Among these polyolefin resins, a resin produced by polymerization using a single-site catalyst is particularly preferable in the present invention because it is inexpensive, has good photographic properties, good suitability for disposal, and has excellent various properties.

As the homopolyethylene resin, a radical initiator such as oxygen or peroxide may be used.
A low-density branched polyethylene resin having a long-chain branching density of 0.910 to 0.925 g / cm ³ , produced by a method of polymerizing ethylene under a temperature and pressure condition of 1000 to 3000 kg / cm ^2. Using a Ziegler catalyst (Ti-based) or a Phillips catalyst (Cr-based) of the medium / low pressure method,
Linear high-density polyethylene having a linear density of 0.941 to 0.965 g / cm ³ , produced by a method of polymerizing ethylene under the conditions of 50 to 250 ° C. and a temperature and pressure of 50 to 200 kg / cm ^2. Resin, a high-pressure method, a medium-low-pressure method, and a low-density polyethylene produced by blending the low-density polyethylene resin and the high-density polyethylene resin to a density of 0.926 to 0.940 g / cm ^3. There is a resin. Furthermore, there are homopolyethylene resins of various densities in which the molecular weight distribution has been reduced using a metal metallocene polymerization catalyst, which has recently been studied for practical use.

The metallocene catalyst is composed of zirconocene dichloride and methylaminoxan having a uniform active site and discovered by Prof. Kaminsky of Germany, and various patents have been published. Representative examples are JP-A-50-35007 and JP-A-60-35008.
JP, JP-A-60-35009, JP-A-3-2
No. 07703, JP-A-3-234711, JP-A-4-300667 and the like.

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. It has 2-3 times the impact strength and tear strength. Excellent transparency and gloss. Excellent blocking resistance (less low-molecular-weight, low-density components called stickiness components). Low melting point and excellent low temperature heat sealability. Excellent flexibility.

The polymerization method using the metallocene catalyst is disclosed in many patent publications as exemplified below.

JP-A-58-19309, JP-A-58-19309
0-862, JP-A-60-35006, JP-A-60-35007, JP-A-60-35008
JP-A-60-106008, JP-A-60-106008,
-137911, JP-A-61-31404, JP-A-61-108610, JP-A-61-2
No. 21207, JP-A-61-264010,
JP-A-61-29609, JP-A-63-610
No. 10, JP-A-63-152608, JP-A-63-178108, JP-A-63-222177
JP, JP-A-63-222178, JP-A-63-222178
JP-A-222179, JP-A-63-264606, JP-A-63-28070, JP-A-63-50
No. 1369, Japanese Patent Application Publication No. 64-6003, Japanese Patent Application Publication No. 64-45406, Japanese Patent Application Laid-Open No. 64-74202, Japanese Patent Application Laid-Open No. 1-1407, and Japanese Patent Application Laid-Open No. 1-9511.
0, JP-A-1-101315, JP-A-1-101315
129003, JP-A-1-207248,
JP-A-1-210404, JP-A-1-25140
No. 5, JP-A-1-259004, JP-A-1-259004
275609, JP-A-1-301704,
JP-A-1-319489, JP-A-2-22307
JP, JP-A-2-41303, JP-A-2-17
3110, JP-A-2-302410, JP-A-3-56508, JP-A-3-62806, JP-A-3-66710, JP-A-3-7070
No. 8, JP-A-3-70709, JP-A-3-7
0710, JP-A-3-74412, JP-A-4-8704, JP-A-4-11604, JP-A-4-25514, JP-A-4-213305, JP-A-5-310829 Gazette, JP-A-5-32
0242, JP-A-6-228222, JP-A-9-40793, U.S. Pat.
No. 82, U.S. Pat. No. 4,530,914 and the like.

As the copolymer resin of ethylene and α-olefin, there is L-LDPE resin. This LL
DPE (L inear L ow D ensity P oly
e thylene) resin is called third polyethylene resin, medium low-pressure, low-cost, high-strength resin that meets the needs of the times that energy saving, resource saving having both the advantages of high-pressure two polyethylene resins. This resin is a copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 15 carbon atoms, preferably 4 to 10 carbon atoms by a low-pressure method or a high-pressure improvement method, and has a linear linear structure having a short branch. It is a polyethylene resin. Preferred α-olefins in terms of physical strength and cost include butene-1, octene-1, hexene-1,4-methylpentene-1, and heptene-1. Particularly, an ethylene / α-olefin random copolymer resin is preferable in the present invention, but an ethylene / α-olefin block copolymer resin or a mixed resin of these two types can also be used.

Typical L-LDPE resin polymerization processes include a gas phase method using a medium / low pressure apparatus, a solution method, a liquid phase slurry method, and an ionic polymerization method using a high pressure improvement apparatus.

Specific examples of the L-LDPE resin are shown below. Ethylene / butene-1 copolymer resin G resin and NUC-FLX (UCC) Dourex (Dow Chemical) Screer (DuPont Canada) Marlex (Philips) Stamirex (DSM) Exelen VL (Sumitomo Chemical) Neozex (Mitsui Petrochemical) Mitsubishi Polyethylene-LL (Mitsubishi Yuka) Nisseki Linirex (Nippon Petrochemical) NUC Polyethylene-LL (Nippon Unicar) Idemitsu Polyethylene L (Idemitsu Petrochemical) Ethylene / Hexene-1 copolymer resin TUFLIN ( (UCC) TUFTHENE (Nihon Unicar) Ethylene / 4-methylpentene-1 copolymer resin Ultzex (Mitsui Petrochemical) Ethylene / octene-1 copolymer resin Stamirex (DSM) Dourex (Dow Chemical) Screer ( Dupo Canada Inc.) MORETEC (Idemitsu Petrochemical)

Among these L-LDPE resins, a resin preferable for use in a film-like packaging material particularly required for tear strength and impact piercing strength has a melt flow rate (hereinafter referred to as MFR) of 0.1. 1 to 40 g / 10 min (measured under condition 4 of JIS K-7210; test temperature 19)
0 ° 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, L of Sumikasen-L (Sumitomo Chemical), Nipolon L (Tosoh), Ubepolyethylene (Ube Industries) and the like obtained by the improved high pressure method process which reduced the equipment cost by converting the conventional high pressure method manufacturing process.
-LDPE resins are also preferred.

A particularly preferred representative example is given by a trade name, in which polyethylene has 6 carbon atoms as an α-olefin side chain.
Petrochemical Co., Ltd. introduced 4-methylpentene-1
MORETEC of Idemitsu Petrochemical Co., Ltd., which introduced octene-1 having 8 carbon atoms as an α-olefin side chain, Stamirex of DSM, and Dourex of Dow Chemical Co., Ltd. It is an L-LDPE resin obtained by the company liquid phase process.) Preferable representative examples obtained by the gas phase process of the low pressure method are listed below under trade names: TUFLIN of Nippon Unicar Co., Ltd., in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain.
And TUFTHENE of UCC.

The recently released density ranges from 0.87 to 0.8.
Ultra low density linear low density polyethylene resin of 910 g / cm ³ , for example, NUC-FLX of UCC or Sumitomo Chemical
Exelen VL of Co., Ltd. is also preferable (the above two products use butene-1 having 4 carbon atoms in the α-olefin).

The ratio of ethylene to α-olefin is preferably 70% or more, more preferably 80% or more. When the ethylene content is less than 70%, the polymerization suitability deteriorates and the cost increases, and the obtained ethylene / α-olefin copolymer resin has high tackiness and deteriorates the film moldability, resulting in large blocking between films. It is difficult to put it to practical use except for the application in which the innermost layers used as the innermost layer of the multilayer co-extruded blown film are used as a blocking adhesive laminated film.

As the homopolypropylene resin, a Ziegler catalyst (Ti-based) is mainly used.
~35kg / cm density produced by polymerizing propylene at a temperature and pressure of ² 0.890~0.910g / cm ³
Resin. 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.

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 may be set to 0.1 in terms of the balance between rigidity, physical strength, and production suitability.
5 to 30% by weight is preferable, and 1 to 20% by weight is more preferable.

The α-olefin in the copolymer resin of propylene and α-olefin is the same as the α-olefin used 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 which has a large adverse effect on the photographic 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. A special example 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 as a titanium compound,
TiBr, titanium tetrahalides such as TiI _4, Ti
(OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl _3, etc., trihalogenated alkoxytitanium, Ti (OCH ₃ ) ₂ Cl ₂ , T
_{i (OC 2 H 5) 2} Cl 2, Ti (OC 2 H 5) dihalide such as ₂ Br ₂ alkoxy _{titanium, Ti (OCH 3) 3 Cl} ,
There are monohalogenated trialkoxy titanium such as Ti (OC ₂ H ₅ ) ₃ Cl and Ti (OC ₂ H ₅ ) ₃ Br.

Examples of the organomagnesium compound include ethylbutylmagnesium, diisobutylmagnesium, dihexylmagnesium, ethylmagnesium chloride, and MgF ₂ , MgCl ₂ , MgBr ₂ , and MgI ₂ .
Examples of the vanadium compound include vanadium tetrachloride, vanadium oxytrichloride, diethoxymonochloride vanadate, and diethoxydichloride vanadate. These halogen compounds and metal compounds adversely affect the photographic properties of the silver halide photographic light-sensitive material.
One or more of the zeolite and the hydrotalcite compound is used in a total amount of 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 molded article for a photographic light-sensitive material of the present invention is injection-molded using only a polyolefin resin, the molecular weight distribution is preferably 1.5 to 7.0, more preferably 2.0 to 6.5, and 2.5. ~ 6.0 is most preferred. If the molecular weight distribution is less than 1.5, 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. Also, MFR
(Measured at a test temperature of 190 ° C. and a test load of 2.16 kgf under the E condition of ASTM D1238) is preferably 5 to 70 g / 10 min, more preferably 7 to 50 g / 10 min, and most preferably 10 to 40 g / 10 min. If it is less than 5 g / 10 minutes, molding failures (short shots, weld lines, etc.) frequently occur, and the molding cycle becomes longer, making it impossible to put it to practical use. On the other hand, if the melt flow rate exceeds 70 g / 10 minutes, the fluidity of the resin becomes too large, and the physical strength is too small to be practically used.

The acid-modified polyolefin resin is a modified polyolefin resin obtained by graft-modifying a polyolefin resin and an unsaturated carboxylic acid, and examples thereof include a graft-modified polyethylene resin, a graft-modified polypropylene resin, and a graft-modified ethylene copolymer resin (EVA resin). ,
EEA resin, L-LDPE resin, EMA resin, etc.).

The unsaturated carboxylic acids graft-modified with the polyolefin resin are generically referred to, including their derivatives. Typical examples thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, Mesaconic acid, angelic acid, citraconic acid, crotonic 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 them, acrylic acid, maleic acid, maleic anhydride and nadic acid are preferred, and maleic anhydride is particularly preferred.

The method for graft-modifying unsaturated carboxylic acids in the acid-modified polyolefin resin is not particularly limited. For example, the reaction in the molten state
No. 421, etc., the method disclosed in Japanese Patent Publication No. 44-15422, which reacts in a solution state, the method disclosed in Japanese Patent Publication No. Tokubo 50-7 to react in the state
There is a method disclosed in, for example, US Pat. Among these methods, the melt kneading method using an extruder is preferable because it is simple in operation and inexpensive.

The amount of the unsaturated carboxylic acids to be used depends on the polyolefin resin base polymer (various polyethylene resins, various polypropylene resins, various polyolefin copolymer resins, polybutene-1 resin, poly-4-methylpentene-
1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 10 parts by weight, based on 100 parts by weight of an α-olefin homopolymer resin such as 1 and a copolymer resin thereof).
5 parts by weight.

An organic peroxide or the like is used to promote the reaction between the polyolefin resin and the unsaturated carboxylic acids.

Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, dicumyl peroxide, α,
α'bis (t-butylperoxydipropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) Oxy) hexyne, di-t-butyl peroxide, cumene hydroperoxide, t-butyl-hydroperoxide, dicumyl peroxide, t-butylperoxylaurate, t-butylperoxybenzoate, 1,3bis ( organic peroxides such as t-butylperoxyisopropyl) benzene, cumene hydroperoxide, di-t-butyl-diperoxyphthalate, t-butylperoxymaleic acid and isopropyl percarbonate; and azobisisobutyronitrile. Examples include azo compounds and inorganic peroxides such as ammonium persulfate.

These may be used alone or in combination of two or more. Particularly preferred is a decomposition temperature of 170 ° C.
Di-t-butyl peroxide which is between ２００200 ° C.
Di-cumyl peroxide, 2,5-dimethyl-2,5
Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5 di (t-butylperoxy) hexyne, 1,
3-bis (t-butylperoxyisopropyl) benzene.

The amount of these peroxides to be added is not particularly limited, but is based on 100 parts by weight of the polyolefin resin.
It is 0.005 to 5 parts by weight, preferably 0.01 to 1 part 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.

Further, the acid-modified polyolefin resin can coat and uniformly disperse the surface of a light-shielding substance such as carbon black or aluminum powder or a fibrous filler contained in the film, thereby reducing the generation of microgrids. By doing so, the physical strength of the film can be improved.

The resin composition used in the molded article of the present invention contains at least one of a lubricant, a surfactant and an antioxidant. By containing at least one of these lubricants, surfactants and antioxidants, physical strength, moldability, antistatic properties and the like are improved, and deterioration due to heat is prevented.

The total content of at least one of the lubricant, the surfactant and the antioxidant is 0.001 to 20 parts by weight, preferably 0.0 to 20 parts by weight, based on 100 parts by weight of the thermoplastic resin.
05 to 15 parts by weight, more preferably 0.01 to 10 parts by weight, particularly preferably 0.02 to 5 parts by weight, most preferably 0.04 to 2.5 parts by weight. When the content is less than 0.001 part by weight, the effect of the addition is not effectively exhibited, and only the kneading cost is required. When the content exceeds 20 parts by weight, the screw of the extruder is used. The occurrence of slip increases, the supply of a uniform amount of resin becomes impossible, and molding failure occurs frequently, making production difficult.In addition, the amount of bleed-out increases over time, and the amount adheres to the photosensitive layer of the photographic photosensitive material, thereby inhibiting development. May cause a failure.

Lubricants include injection moldability improvement, lubricity improvement, light-shielding substances, fibrous or non-fibrous fillers, and hydrous double salt compounds.
(Typical examples are hydrotalcite compounds) .As a result, improved photographic properties, improved appearance of injection molded articles, improved antistatic properties, reduced drawing torque of photographic film, Many effects such as prevention of scratch generation, improvement of abrasion resistance, and improvement of fluidity of the resin composition can be achieved.

The amount of the lubricant added is preferably 0.01 to 15% by weight, more preferably 0.03 to 10% by weight, and most preferably 0.05 to 5% by weight. When the total content is less than 0.01% by weight, there is almost no effect of improving the above properties, and only the kneading cost increases. If the total content exceeds 15% by weight, slippage with the screw of the extruder increases, and it becomes impossible to supply a uniform amount of resin, and molding failure occurs frequently, making production difficult. further,
Over time, the amount of bleed-out increases, and the bleed-out may adhere to the photosensitive layer of the photographic light-sensitive material and cause failure such as development inhibition.

Representative commercial lubricant names and manufacturer names are described below.

(1) Fatty acid amide-based lubricant; [Saturated fatty acid amide-based lubricant] Behenic acid amide-based lubricant; Diamid KN (Nippon Kasei), etc. Stearamide-based lubricant; Armide HT (Lion fat), Alflo S-10 ( Nippon Yushi), fatty acid amide S (Kao), Diamid 200 (Nippon Kasei), Diamid AP-1 (Nippon Kasei), Amide S
・ Amide T (Nitto Kagaku), Neutron-2 (Nippon Seika), etc. [Hydroxystearic acid amide lubricant] Palmitic amide lubricant; Neutron S-18
(Nippon Seika), Amide P (Nitto Chemical), etc. Lauric amide-based lubricants; Armide C (Lion Akzo), Diamond (Nippon Kasei), etc. [Unsaturated fatty acid amide-based lubricants] Erucamide amide-based lubricant; Alflow P -10 (Nippon Yushi), Neutron-S (Nippon Seika), LUBROL
(I ・ C ・ I), Diamid L-200 (Nippon Kasei)
Oleic acid amide lubricants; Armoslip CP (Lion Akzo), Neutron (Nippon Seika), Neutron E-18 (Nippon Seika), Amide O (Nitto Kagaku), Diamid O-200, Diamid G-200 (Nippon Kasei), Alflo E-10 (Nippon Oil & Fats), fatty acid amide O (Kao), etc. [Bis fatty acid amide lubricant] Methylene bisbehenic amide lubricant; Diamid NKbis (Nippon Kasei), etc. Methylene bis stearamide amide lubricant; Diamid 200 bis (Nippon Kasei), Armowax (Lion Akzo), Bisamide (Nitto Chemical), etc. Methylene bis oleamide amide lubricant; Lubron O
(Nippon Kasei) etc. Ethylene bis stearamide amide lubricant; Armoslip EBS (Lion Akzo) etc. Hexamethylene bis stearamide amide lubricant; Amid 65 (Kawaken Fine Chemical) etc. Hexamethylene bis oleamide amide lubricant; Amide 60 (Kawaken Fine Chemical), etc.

(2) Nonionic surfactant lubricant; Electrostripper-TS-2, Electrostripper-T
S-3 (Kao soap) etc.

(3) Hydrocarbon lubricant; liquid paraffin,
Natural paraffin, microwax, isoparaffinic synthetic petroleum hydrocarbon, synthetic paraffin, polyethylene wax (number average molecular weight of 10,000 or less, preferably 8,000 or less, particularly preferably 6,000 or less), polypropylene wax (number average) The molecular weight is 10,000 or less, preferably 8,000 or less, particularly preferably 6,000 or less.), Chlorinated hydrocarbons, fluorocarbons, and the like.

(4) Fatty acid-based lubricants; higher fatty acids (C12
To 35 are preferred, specifically, caproic acid, stearic acid, oleic acid, erucic acid, palmitic acid, etc.), oxy fatty acids, etc.

(5) Ester lubricants: lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, etc.

(6) Alcohol-based lubricant; polyhydric alcohol, polyglycol, polyglycerol, etc.

(7) Fatty acid metal salt lubricant (metal soap); lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid Acids, higher fatty acids such as erucic acid and Li, Na, M
g, Ca, Sr, Ba, Zn, Cd, Al, Sn, P
Compounds with metals such as b, Cd and the like are mentioned, and preferred are magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate, zinc oleate, magnesium oleate and the like.

(8) Partially saponified montanic acid ester;

(9) Silicone-based lubricants: Various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Toray Silicone), especially various silicone oils, not only exhibit the effects of improving resin fluidity and lubricity, but also When used in combination with a light-shielding substance, the dispersibility of the light-shielding substance is
Haze (ASTM D-100)
As a result of increasing 3), unexpected effects such as improvement in coloring power and improvement in light-shielding properties are exhibited, which is preferable.

The silicone oil preferably has a viscosity at room temperature in the range of 50 to 100,000 centistokes, and more preferably 5,000 to 30,000.
Centistokes, most preferably 8,000 to 25.0
A high viscosity of 00 centistokes is preferred. Specific examples of silicone and silicone-modified products include polymethylphenylsiloxane, olefin-modified silicone, amide-modified silicone, polydimethylsiloxane, amino-modified silicone, carboxyl-modified silicone, α-methylstyrene-modified silicone, polyethylene glycol and polypropylene glycol. Polyether-modified silicone, olefin / polyether-modified silicone,
It is a silicone oil containing a modified siloxane bond such as an epoxy-modified silicone, an amino-modified silicone, and an alcohol-modified silicone. Among the silicone oils, olefin-modified silicones, amide-modified silicones, polydimethylsiloxanes, which do not adversely affect the photographic light-sensitive material and have a high lubricating effect, particularly when applied to injection molded articles for photographic light-sensitive materials, are preferred. Polyether-modified silicone and olefin / polyether-modified silicone.

The effects of the addition of silicone oil are as follows. (1) fibrous filler (filler), non-fibrous filler,
The surface of these materials is coated simply by using them together with a light-shielding substance and a pigment to improve dispersibility. (2) Improve the fluidity of the resin, reduce the motor load on the screw, and prevent the occurrence of melt fracture. (3) Sufficient lubricity can be ensured without adding a fatty acid amide that bleeds out to form a white powder. (4) Reduce the friction coefficient of the injection molded product even in the heated state. (5) When used in combination with a light-shielding substance, the thermoplastic resin becomes cloudy and the haze is increased. As a result, the coloring power can be improved and the light-shielding ability can be improved. Nature can be secured.

Among the above lubricants, various saturated fatty acid amide-based lubricants, various unsaturated fatty acid amide-based lubricants, and silicone-based lubricants are preferable for the purpose of improving the lubricating property. Improvement of dispersibility of fillers and hydrotalcite compounds, etc., improvement of dispersibility of the light-shielding substance and the like by the surface coating and imparting of a hygroscopicity lowering effect, for the purpose of improving resin fluidity, ester lubricants, fatty acid metal salts,
Alcohol-based lubricants, hydrocarbon-based lubricants, and fatty acid-based lubricants are preferable. Among the fatty acid metal salts, halogen compounds and metal compounds (including polymerization catalysts) that adversely affect the photographic properties of photographic light-sensitive materials are neutralized, and photographic sensitization is performed. Calcium stearyl lactate, calcium stearate, magnesium stearate, and zinc stearate are preferred, and magnesium stearate and zinc stearate are particularly preferred because they render the material harmless. In the case of a thermoplastic resin that polymerizes using a catalyst, a catalyst residue is present in the resin and adversely affects the photographic properties of the photographic light-sensitive material, causing rust in the molding die. Therefore, use a fatty acid metal salt-based lubricant (metal soap). 0.001
To 15% by weight, preferably 0.003 to 10% by weight, particularly preferably 0.005 to 5% by weight.

The surfactant can ensure antistatic and improved lubricity. Further, the dispersibility of aluminum powder, a light-shielding substance, a hydrous double salt compound (a typical example is a hydrotalcite compound) in a molded article can be improved.

Representative examples of the surfactant are shown below. The amount of the surfactant to be added is preferably 0.01 to 5.0% by weight, more preferably 0.05 to 3.0% by weight, and 0.1 to 5.0% by weight.
~ 1.5 wt% is most preferred. When the addition amount is less than 0.01% by weight, the above-mentioned effects cannot be sufficiently exerted, and only kneading costs are required.
Over time, the amount of bleed-out increases, which may adversely affect the photographic properties of the photographic material.

Representative examples of the nonionic surfactant are shown below. Polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamine fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene Glycerin fatty acid ester, polyoxyethylene fatty amine, sorbitan monofatty acid ester, fatty acid ventaerythrit, fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct,
Fatty acid amino or fatty acid amide ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkyl naphthol ethylene oxide adduct,
An ethylene oxide adduct of a partial fatty acid ester of a polyhydric alcohol, polyoxyethylene alkyl amide,
Alkylamine derivatives, other JP-B-63-26697
No. 120, various nonionic antistatic agents and the like.

Representative examples of the anionic surfactant are shown below. Ricinoleic acid sulfate soda salt, various fatty acid metal salts, silinoleic acid ester soda ester salt, sulfated ethyl aniline sulfate, olefin sulfate salt, oleyl alcohol sulfate soda salt, alkyl sulfate ester salt, fatty acid ethyl sulfonate , Alkyl sulfate, alkyl phosphate, alkyl sulfonate, alkyl naphthalene sulfonate, alkyl benzene sulfonate, succinate sulfonate, phosphate ester salt and the like.

Representative examples of the cationic surfactant are shown below. Primary amine salts, tertiary amine salts, quaternary ammonium salts, trialkylbenzylammonium salts, pyridine derivatives and the like.

Representative examples of the amphoteric surfactant are shown below. Carboxylic acid derivatives, imidazoline derivatives, betaine derivatives and the like.

Further, 776-Plastic Data Handbook (published on April 5, 1984 by the KK Industrial Research Council)
It is possible to select and use the type and the amount of addition from the various antistatic agents disclosed on page 778.

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

The antioxidant will be described. The oxidative decomposition of the resin is higher for polyolefin resins having more CH ₃ branches. This is because the amount of oxygen absorption is large. Therefore, the degree of oxidative decomposition is as follows: polypropylene resin> homopolyethylene resin> ethylene / α-olefin copolymer resin.
Various polyethylene resins that are thermoplastic resins (ethylene
Alpha-olefin copolymer resins and various polypropylene resins (including propylene / ethylene (random and block) copolymer resins) are hydrocarbons, and the autoxidation of hydrocarbons is dehydrated in the presence of oxygen. It is believed that once free radicals are generated, they proceed in a chained manner as follows.

RH → R ・ R ・ + O ₂ → ROO ・ ROO + RH → ROOH + R ・ ROOH → RO ・ + ・ OH RO ・ + RH → ROH + R ・ OH + RH → HOH + R ・

In this way, the oxidation of hydrocarbons is stopped at an accelerated rate to produce a large amount of alcohols, aldehydes, acids, etc., which adversely affect the photographic properties of the photographic light-sensitive material. make.

In order to prevent the oxidation of hydrocarbons, it is necessary to complete the above-mentioned chain reaction, for which an antioxidant or a radical scavenger is used. That is, the antioxidant decomposes a free radical chain terminator that reacts with free radicals (mainly ROO.) As a chain propagator to deactivate the free radicals and hydroperoxide ROOH that is a main source of free radicals. Then, there is a peroxide decomposer that stabilizes this. The former includes an alkylphenol-based antioxidant and an aromatic amine-based antioxidant. The latter includes a sulfur-based antioxidant and a phosphorus-based antioxidant. In order to prevent yellowing or browning due to thermal deterioration of the thermoplastic resin and occurrence of lumps (foreign-like black hardening), it is preferable to use a free radical chain termination antioxidant and a peroxide decomposition antioxidant in combination. . Since various antioxidants are also reducing agents that have an adverse effect on the photographic light-sensitive material, if the type and the amount of addition are not carefully determined and selected, the quality of the photographic light-sensitive material is greatly deteriorated, causing a problem.

The addition amount of the antioxidant varies depending on the cost, the size of the effect and the adverse effect on the photographic properties of the photographic light-sensitive material, but is preferably 0.0001 to 5.0% by weight. 0.0005-3.0% by weight is preferred,
0.001 to 1.0% by weight is more preferable, and 0.005 to 1.0% by weight.
~ 0.5% by weight is most preferred. 0.0001 added
When the amount is less than 5% by weight, there is no effect of addition and only the kneading cost is required. When the amount exceeds 5.0% by weight, even an antioxidant having a small effect and effect utilizes the oxidation and reduction effects. It may adversely affect the photographic properties of the photographic light-sensitive material and bleed out to the surface of the injection-molded article to deteriorate the appearance.

Representative examples of the antioxidant used in the present invention are shown below.

(A) A phenolic antioxidant (t is te
Vitamin E (tocopherol), 6-t-butyl-3-
Methylphenyl derivative, 2,6-di-t-butyl-P
-Cresol, 2,6-di-t-butyl-phenol,
2,6-di-t-butyl-α-dimethylamino-p-cresol, 2,6-di-t-butyl-p-ethylphenol, 2,2′-methylenebis- (4-ethyl-6-t-
Butylphenol), 4,4'-butylidenebis (6-t
-Butyl-m-cresol), 4.4′-thiobis (6-
t-butyl-m-cresol), 4,4-dihydroxydiphenylcyclohexane, butylated hydroxyanisole, alkylated bisphenol, styrenated phenol, 2,6-di-t-butyl-4-methylphenol,
2,6-di-t-butyl-4-ethylphenol, n-
Octadecyl-3- (3'.5'-di-t-butyl-4 '
-Hydroxyphenyl) propinate, 2.2′-methylenebis (4-methyl-6-t-butylphenol),
4.4'-thiobis (3-methyl-6-t-butylphenyl), 4,4'-butylidenebis (3-methyl-6-t
-Butylphenol), 4.4′-thiobis (3-methyl-6-t-butylphenol), stearyl-β (3
-5-di-t-butyl-4-hydroxyphenyl) propionate, 1.1.3-tris (2-methyl-4hydroxy-5-t-butylphenyl) butane, 1.3.5
Trimethyl-2,4,6-tris (3.5-di-tert-butyl-4hydroxybenzyl) benzene, tetrakis [methylene-3 (3.5-di-tert-butyl-4-hydroxyphenyl) propionate] methane etc

(B) Ketone amine condensation antioxidant 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, polymer of 2,2.4, trimethyl-1,2-dihydroquinoline, trimethyl Dihydroquinoline derivatives, etc.

(C) Allylamine antioxidant phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-phenyl-N′-isopropylidyl-P
-Phenylenediamine, NN'-diphenyl-P-phenylenediamine, NN'-di-β-naphthyl-P-
Phenylenediamine, N- (3'-hydroxybutylidene) -1-naphthylmin and the like

(D) Imidazole antioxidants 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, etc.

(E) Phosphite antioxidants Alkylated allyl phosphite, tris (mono and / or dinonyl phenyl) phosphite, cyclic neopentanetetrayl bis (2.6-di-t-butyl-4)
-Methylphenyl) phosphite, diphenylisodecylphosphite, tris (nonylphenyl) phosphite sodium phosphite, tris (nonylphenyl) phosphite, 2.2-methylenebis (4.6-di-t-butylphenyl) Octyl phosphite, Tris (2.4
-Di-t-butylphenyl) phosphite, triphenyl phosphite, etc.

(F) Thiourea antioxidants Thiourea derivatives, 1,3-bis (dimethylaminopropyl) -2-thiourea, etc.

(G) Other antioxidants useful for air oxidation: dilauryl thiodipropionate, etc.

Representative examples of the most preferred hindered phenolic antioxidants for the present invention are shown below. 1,3,5-trimethyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ′ · 5′-di-tert-butyl) -4 '
-Hydroxyphenyl) propionate] methane, octadecyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 2,2 ', 2'-tris [(3,5-di-tert-butyl-4 -Hydroxyphenyl) propionyloxy] ethyl isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-di-methylbenzyl) isocyanurate, tetrakis (2,4-di-tert. -Butylphenyl) 4,4′-biphenylenediphosphite,
4'-thiobis- (6-tert-butyl-O-cresol), 2,2'-thiobis- (6-tert-butyl-
4-methylphenol), tris- (2-methyl-4-
(Hydroxy-5-tert-butylphenyl) butane;
2,2'-methylene-bis- (4-methyl-6-tert
-Butylphenol), 4,4'-methylene-bis-
(2,6-di-tert-butylphenol), 4,4 '
-Butylidenebis- (3-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-
Methylphenol, 4-hydroxymethyl-2,6-
Di-tert-butylphenol, 2,6-di-ter
t-4-n-butylphenol, 2,6-bis (2'-hydroxy-3'-tert-butyl-5'-methylpentyl) -4-methylphenol, 4,4'-methylene-bis- (6-tert -Butyl-O-cresol), 4,
4'-butylidene-bis (6-tert-butyl-m-
Cresol), 3,9-bis {1.1-dimethyl-2-
[Β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl {2,4,8,1
0-tetraoxaspiro [5,5] undecane and the like. Among these, antioxidants having a melting point of 100 ° C. or higher, preferably 110 ° C. or higher, particularly preferably 120 ° C. or higher, and most preferably 130 ° C. or higher. It is effective to use a phenolic antioxidant and a phosphorus antioxidant in combination.

The vitamin E (tocopherol), when used in combination with a light-shielding substance such as carbon black, in addition to its antioxidant effect, improves the light-shielding ability as compared with the case where a light-shielding substance such as carbon black is added alone, and has a dispersibility. Therefore, even if the amount of the light-shielding substance is reduced by 10% or more, it is possible to obtain a molded article having the same light-shielding property, and various effects such as an improvement in physical strength, an improvement in appearance, and a reduction in material cost are exhibited. This is preferred.

Typical commercial antioxidants are shown below.

(1) Phenolic antioxidant; SUMI
LIZER BHT (Sumitomo), YOSHINOX BH
T (Yoshitomi), IRGANOX 1076 (Ciba Geigy), MARK AO-50 (Adeka Argus), S
UMILIZER BP-76 (Sumitomo), TOMINO
X SS (Yoshitomi), IRGANOX 565 (Ciba Geigy), NONOX WSP (ICI), SANTONOX
(Monsanto), SUMILIZER WX R
(Sumitomo), ANTAGECRYSTAL (Kawaguchi), IRGA
NOX 1035 (Ciba Geigy), ANTAGE W-
400 (Kawaguchi), NOCLIZER NS-6 (Ouchi Shinko), IRGANOX 1425 WL (Ciba Geigy), MARK AO-80 (Adeka Argus), SU
MILIZER GA-80 (Sumitomo), TOPANOL
CA (ICI), MARK AO-30 (Adeka Argus), MARK AO-20 (Adeka Argus),
IRGANOX 3114 (Chiba Geigy), MARK
AO-330 (Adeka Argus), IRGANOX 1
330 (Ciba Geigy), CYANOX 1790 (AC
C), IRGANO 1010 (Ciba Geigy), MA
RK AO-60 (ADEKA Argus), SUMILI
ZER BP-101 (Sumitomo), TOMINOX TT
(Yoshitomi) etc.

(2) Phosphorus antioxidant; IRGAFOS
168 (Ciba Geigy), MARK 2112 (ADEKA
Argus), Weston 618 (BorgWarner), MARK PEP-8 (Adeka Argus), U
LTRANOX 626 (Borg Warner), MARK
PEP-24G (Adeka Argus), MARK PE
P-36 (Adeka Argus), HCA (Sanko), etc.

(3) Thioether antioxidants; DLT
DP "YOSHITOMI" (Yoshitomi), SUMILIZ
ER TPL (Sumitomo), ANTIOX L (NOF), DM
TD "YOSHITOMI" (Yoshitomi), SUMILIZ
ER TPM (Sumitomo), ANTIOX M (NOF), DST
P “YOSHITOMI” (Yoshitomi), SUMILIZE
RTPS (Sumitomo), ANTIOXS (NOF), SEEN
OX 412S (Cipro), MARK AO-412S
(Adeka Argus), SUMILIZER TP-D
(Sumitomo), MARK AO-23 (Adeka Argus), S
ANDSTAB P-EPQ (sand), IRGAFOS
P-EPQ FF (Ciba Geigy), IRGANOX 1
222 (Ciba Geigy), MARK 329K (ADEKA
Argus), Weston 399 (Borg Warner), MARK 260 (Adeka Argus), MAR
522A (Adeka Argus) etc.

(4) Metal deactivator NAUGARD XL-1 (Uniroyal), MARK
CDA-1 (ADEKA Argus), MARK CDA-
6 (Adeka Argus), LRGANOX MD-10
24 (Ciba Geigy), CUNOX (Mitsui Toatsu), etc.

The phenolic antioxidant is particularly preferable because it hardly adversely affects the photographic properties of the photographic light-sensitive material, improves the light-shielding ability by coloring over time, and is relatively inexpensive. Are various types of Irganox from Ciba-Geigy and Sumiliz from Sumitomo Chemical Co., Ltd.
er BHT, Sumilizer BH-76, Sum
ilizer WX-R, Sumilizer BP-1
01 and so on. Also, 2,6-di-hybutyl-p-cresol (BHT), a low volatility high molecular weight phenolic antioxidant (trade name: Ireganox 1010, Ire)
ganox 1076, Topanol CA, Iono
x 330), dilauryl thiodipropionate, distearyl thiopropionate, dialkyl phosphate and the like, and it is effective to use two or more thereof in combination.

In particular, at least one of the above hindered phenolic antioxidants having a melting point of 100 ° C. or higher, preferably 110 ° C. or higher, particularly preferably 120 ° C. or higher, and most preferably 130 ° C. or higher, which is a typical example of a free radical chain terminator. The combined use of one type and at least one type of a phosphorus-based antioxidant as a peroxide decomposer can prevent the resin and additives from thermally deteriorating without significantly deteriorating the photographic properties of the photographic material. It is preferable because it can be increased.

The most preferred antioxidant to be contained in the molded article of the present invention is tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxy-phenyl) propionate] methane, n-octadecyl-
3- (4'-Hydroxy-3 ', 5'-di-t-butylphenol) propionate and tris- (2,4-di-t-
(Butylphenyl) phosphite. It is preferable to contain at least one or more of them at 0.0005 to 1.5% by weight.

The representative general formula of the organic cyclic phosphorus compound which is one of the preferred phosphorus antioxidants among the antioxidants of the present invention is described below.

[0100]

Embedded image {Wherein, R ₁ represents a tert-butyl or tert-amyl, R ₂ represents an alkyl group having 1 to 9 carbon atoms, R ₃
Represents a hydrogen atom or an alkyl group having 1 to ₄ carbon atoms, and R ₄ represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 15 carbon atoms. ｝

[0101]

Embedded image In the formula, R ₂ represents an alkyl group having 1 to 9 carbon atoms,
R ₃ represents a hydrogen atom or an alkyl group having 1 to ₄ carbon atoms, and R ₄ represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 15 carbon atoms. ｝

[0102]

Embedded image In the formula, R ₂ represents an alkyl group having 1 to 9 carbon atoms,
R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and M represents an alkali metal. ｝

[0103]

Embedded image中 where R_ThreeIs a hydrogen atom or an alkyl having 1 to 4 carbon atoms
A kill group;_FiveAnd R ₆Are hydrogen atoms and carbon atoms, respectively.
Alkyl group having 1 to 12 children, cycloalkyl group, aryl
X represents an -OH group or-
Shows O-NH4 +. ｝

In addition, various antioxidants and plastic additives disclosed on pages 794 to 799 of the Plastic Data Handbook (published by the KK Industrial Research Association), and various types disclosed on pages 327 to 329 of the Plastic Additives Data Collection (KK Chemical Industry Co., Ltd.) Antioxidants and PLASTICS AGE ENCY
There are various antioxidants disclosed on pages 211 to 212 of CLOPEDIA Advanced Edition, 1986 (KK Plastic Age), which can be selected from the effects on photographic properties and antioxidant effects. The use of these antioxidants alone or in combination of two or more is essential in the present invention so as not to adversely affect the photographic properties. It is preferable to maintain

The resin composition used in the molded article for a photographic light-sensitive material of the present invention contains one or more plasticizers. By including a plasticizer, the dispersibility of a light-shielding substance, a lubricant, a surfactant, an antioxidant, and the like can be improved, and bleed-out resistance can be improved.

The content of one or more plasticizers is 0.1 to 150 parts by weight, preferably 0.5 to 100 parts by weight, more preferably 1 to 80 parts by weight based on 100 parts by weight of the thermoplastic resin. Parts by weight, particularly preferably 2 to 60 parts by weight, most preferably 5 to 50 parts by weight. When the content of the plasticizer is less than 0.1 part by weight, the effect of improving the uniform dispersibility of the light-shielding substance, the lubricant, the surfactant, the antioxidant, and the like is small, and only the kneading cost is increased. On the other hand, if it exceeds 150 parts by weight, it is impossible to extrude a stable amount of resin due to a decrease in physical strength or a slip with an extruder screw.

The following are typical examples of the plasticizer. (1) phthalic acid plasticizer dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diisodecyl phthalate, butyl lauryl phthalate, ditridecyl phthalate, butyl benzyl phthalate,
Butyl phthalyl butyl glycolate, etc. (2) Phosphate plasticizers Tricresyl phosphate, trioctyl phosphate, etc. (3) Fatty acid plasticizers Tri-n-butyl citrate, dioctyl adipate, dioctyl azelate, dioctyl sebacate, acetyl Methyl ricinoleate, etc. (4) Epoxy plasticizer Alkyl epoxy stearate, diisodecyl 4,5-epoxytetrahydrophthalate, etc. (5) Bis [2- (2-butoxyethoxy) ethyl] adipate compound, bis (2-butoxyethyl) ) Phthalate compound, bis [2- (2-butoxyethoxy) ethyl]
Thiodipropionate, bis (2-butoxyethyl) thiopropionate compound, etc. (6) Other plasticizers Chlorinated paraffin, polyester, sucrose octaacetate, etc.

As a plasticizer preferable for the molded article for a photographic light-sensitive material of the present invention, an alicyclic saturated hydrocarbon compound having three or more cyclohexyl rings is preferable. Among them, three plasticizers separated from each other by an alkylene group in the molecule are preferable. Liquid alicyclic saturated hydrocarbon compounds having a cyclohexyl ring as described above are preferred. By using such an alicyclic saturated hydrocarbon compound, the light-shielding substance and the lubricant, the surfactant, the uniform dispersibility of the antioxidant are improved, and the photographic properties, bleed-out resistance, physical strength, moldability, In addition to improving the suitability for recycling and the like, the antistatic property can be improved, and bis [2- (2-
Butoxyethoxy) ethyl] adipate and bis (2-
Particularly, a combination of one selected from butoxyethyl) phthalate compounds and one selected from bis [2- (2-butoxyethoxy) ethyl] thiodipropionate compound and bis (2-butoxyethyl) thiodipropionate compound is particularly preferable. preferable.

When the resin composition used for the molded article for a photographic light-sensitive material of the present invention is required to have a light-shielding property, it may contain a light-shielding substance.

The light-shielding substance will be described.

(1) Inorganic Compound A. Oxides: silica, diatomaceous earth, alumina, titanium oxide, iron oxide (iron black), zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, alumina fiber, etc. Hydroxide: aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, 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 (almond, peanut, fir shell, etc.), cotton, jute, paper strip, non-wood fiber (straw, kenaf, bamboo, esparto) Cellophane pieces, nylon fibers, polypropylene fibers, starch (including modified starch and surface-treated starch), aromatic polyamide fibers and the like.

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 preferred, 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 based on 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 preferable commercial products of carbon black include, for example, carbon black # 2 manufactured by Mitsubishi Kasei.
0 (B), # 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, MA
7, MA8, MA11, MA100, MA100R, M
A220, MA230, # 3050, # 3150, # 3250, # 3600, # as Mitsubishi conductive carbon black
3750, # 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, Cabot Black Pearls L, 2, 46, 70, 71, 7
4,80,81,130,280,430,460,4
80,607,800,880,900,1000,1
100, 1300, 1400, etc., Regal 99, 25
0,300,330,400,415,660,99
1, SRF-S etc., 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, 15,102,3001,3004,3
006,3007,3008,3009,3011,301
2, XC-3016, XC-3017, 3020 and the like. Furthermore, Colombian Chemical's Con
ductex 975, SC, Raven C, H20, 4
10,420,430,450,460,500,52
0,760,790,850,890,1000,10
40,1060,1170,1190,1200,125
0,1255,2000,2500,3500,5000,5
250, 5750, 7000, and the like, but are not limited thereto.

In the present invention, furnace carbon black is preferred for the purpose of improving light-shielding properties, cost and physical properties. As expensive light-shielding substances having an antistatic effect, acetylene carbon black and ketjen carbon which is a modified by-product carbon black are preferred. Black is preferred. Especially high sensitivity
(ISO sensitivity 400 or more) For photographic photosensitive materials, acetylene black having a sulfur content of 0.1% or less is preferable.
The volume resistivity (measured in a thermo-hygrostat at 20 ° C. and 60% RH) is as follows: MFR: 0.3 g / 10 min, density: 0.958
For a film in which 10 parts by weight of Ketjen Black EC is added to 100 parts by weight of high density polyethylene resin of g / cm ³ , 2 × 10 ² Ω · cm and Ketjen Black EC are used.
6 × 10 6 for a film containing 10 parts by weight of 600 JD
^For a film containing ¹ Ω · cm and 10 parts by weight of acetylene black, 3.1 × 10 ⁶ Ω · cm and Vulcan XC-7
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, it is important to select a raw material. 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. If ethylene bottom oil derived from naphtha is used as the raw material, the sulfur content in carbon black is reduced to 0.1% by weight. % Is most preferable.

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 low free sulfur content, carbon black produced using ethylene bottom oil from naphtha is most preferred in the present invention.

Further, the content of cyanide by 4-pyridinecarboxylic acid / pyrazolone absorption spectrometry is 0.01% by weight or less, particularly preferably 0.005% by weight or less, most preferably 0.001% by weight or less. The content is good. Further, the aldehyde compound content by the iodine method is 0.1% by weight or less, particularly preferably 0.05% by weight.
Hereafter, it is most preferable to use carbon black having a content of 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.

Particularly for photographic photosensitive 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 (most commonly used called color compound) (2) Dispersible powder (treated with various surface treatment agents, also called dry color, (3) Paste (Plasticizer etc. dispersed) (4) Liquid (Liquid dispersed in surfactant, also called liquid color) (5) Masterbatch pellets (a light-shielding substance is dispersed at high concentration in the plastic to be colored) (6) Moisturizing granular powder (after light-shielding substance is dispersed at high concentration in plastic (7) Dry powder (normal 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 preferred in terms of cost, prevention of contamination of the work place, 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.

In using the molded article of the present invention as a molded article for a photographic light-sensitive material, the photographic light-sensitive material does not generate fog.
Less increase or decrease in photosensitivity, high light-blocking ability, and hardening of carbon black even when added to the innermost layer
Among carbon blacks, pH (J
6.0 to 9.0, average particle size (measured by electron microscopy) is 10 to 120 mμ, particularly 1
It is preferably from 0 to 80 mμ, and most preferably 10 μm.
６０60 mμ. Among these, volatile components (JI
SK6221) 2.0% or less, DBP oil absorption (measured by JIS K6221 oil absorption method A) 50 ml
Furnace carbon black of / 100 g or more is preferable in that it is inexpensive, does not adversely affect photographic properties, improves light-shielding properties, improves dispersibility, and causes little deterioration in physical properties.
In particular, those obtained from ethylene bottom oil or creosote oil as the raw material oil are preferable, and the most preferable in the present invention is furnace carbon black using ethylene bottom oil obtained from naphtha.

Also, ASTM D 161 in the light-shielding substance
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 and then pulverized. 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 a cyan compound which deteriorates photographic properties in a light-shielding substance (a value obtained by converting the amount of hydrogen cyanide determined by 4-pyridinecarboxylic acid / pyrazolone absorption spectrometry into a ppm unit based on the weight of the light-shielding substance) is 20 ppm Or less, preferably 10 ppm or less, particularly preferably 5 pp
m or less, and most preferably 1 ppm or less. In particular, in the case of a gold-sensitized photographic material, unless it is 1 ppm or less, desensitization is large and practical application is difficult, and it is necessary to add a scavenger or the like.

In the present invention, a scavenger is a compound that converts hydrogen cyanide gas into a photographically inert substance. The scavenger should not release substances that adversely affect the silver halide photosensitive material as a result of capturing the hydrogen cyanide gas. Suitably, the hydrogen cyanide gas scavenger may be selected from inorganic or organic compounds of noble metals. Particularly preferred is palladium (II
Or IV; indicates an oxidation state. The same applies hereinafter), platinum (II or I
V) Compound. Gold (I or III) compounds are also preferred. Rhodium (III), iridium (III or IV) and osmium (II, III or IV) compounds are also effective, but higher amounts are required to achieve equivalent effects. Specific examples of useful inorganic or organic noble metal compounds include, for example, Gmelin Handbook (Gmelin Handbook).
k), commercially available products, synthetic products and in
The in situ synthetic product can be used with a purity that does not adversely affect the photographic light-sensitive material.

Preferred palladium compounds include palladium (II) chloride, palladium (II) bromide, palladium (II) hydroxide, palladium (II) sulfate, palladium (II) thiocyanate, and tetrachloropalladium (II) acid salt. (Sodium salt, potassium salt, ammonium salt), hexachloropalladium (IV) salt, tetrabromopalladium (II) salt, hexabromopalladium (IV) salt, bis (salicylate) palladium (II) salt, bis (Dithiooxalato-S, S ') palladium (II) acid salt, trans-dichlorobis (thioether) palladium (II), tetraamminepalladium (II) salt, dichlorodiamminepalladium (II), dibromodiamminepalladium (II),
Oxalatodiammine palladium (II), dinitrodiamminepalladium (II), bis (ethylenediamine) palladium (II) salt, dichloroethylenediaminepalladium (II), bis (2,2′-pipyridine) palladium (I
I) salts, bis (1,10-phenanthroline) palladium (II) salts, tetranitropalladium (II) salts, bis (glycinato) palladium (II), tetrakis (thiocyanato) palladium (II) salts, dichlorobis (phosphine) ) Palladium (II) acid salt, dichlorobis (phosphine) palladium (II), di-μ-chloro-bis [chloro (phosphine) palladium (II)], di-μ-chloro-
Bis [chloro (arsine) palladium (II)] and dinitrobis (arsine) palladium (II).

Preferred platinum compounds include platinum chloride (II), platinum chloride (IV) and hexafluoroplatinum (I
V), tetrachloroplatinate (II), hexachloroplatinate (IV), trichlorotrifluoroplatinate (IV), tetrabromoplatinate (II), hexabromoplatinate (IV), dibromodichloro Platinate (II), hexahydroxoplatinate (IV), bis (oxalato) platinate (II), dichlorobis (oxalatoplatinate (IV), bis (thiooxalato) platinate (II), bis ( Acetylacetonato) platinum (II), bis (1,1,1,5,
5,5-hexafluoro-2,4-pentanedionato) platinum (II), bis (1,1,1-trifluoro-2,4-pentanedionato) platinum (II), tetrakis (thiocyanato) platinum ( II), hexakis (thiocyanato) platinate (IV), bis {(Z) -1,2-dicyanoethylene-1,2-dithiolato} platinate (II), dichlorobis (diethylsulfide) platinum (II) ), Tetrachlorobis (diethylsulfide) platinum (IV), bis (glycinato) platinum (II), dichloroglycinatoplatinate (II),
Dichlorobis (triethylphosphine) platinum (II), chlorohydridobis (triethylphosphine) platinum (I
I), tetraammineplatinum (II) salt, tetrachloroplatinum
(II) acid salt, dichlorodiammineplatinum (II), trichloroammineplatinum (II) salt, hexaammineplatinum (IV) salt,
Chloropentaammineplatinum (IV) salt, tetrachlorodiammineplatinum (IV), dinitrodiammineplatinum (II), dichlorotetrakis (methylamine) platinum (IV) salt, dichloro (ethylenediamine) platinum (II), bis (ethylenediamine) platinum (II) salt, tris (ethylenediamine)
Platinum (IV) salt, dichlorobis (ethylenediamine) platinum (IV) salt, dichlorodihydroxo (ethylenediamine)
Platinum (IV), tetrakis (pyrimidine) platinum (II) salt, dichlorobis (pyridine) platinum (II), bis (2,2′-pipyridine) platinum (II) salt, tetranitroplatinate (II) salt,
Chlorotrinitroplatinate (II), dichlorodinitroplatinate (II), dibromodinitroplatinate (II), hexanitroplatinate (IV), chloropentanitroplatinate (I
V), dichlorotetranitroplatinate (IV), trichlorotrinitroplatinate (IV), tetrachlorodinitroplatinate (IV), dibromodichlorodinitroplatinate (I
V) acid salt, trichloro (ethylene) platinum (II) salt, di-μ-chloro-bis (chloro (ethylene) platinum (II), t
trans-dichloro (ethylene) (pyridine) platinum (I
I), bis [bis (β-mercaptoethylamine) nickel (II) -S, S "-platinum (II) salt and dichlorodicarbonylplatinum (II).

Compounds of gold (I or III), rhodium (III), iridium (III or IV) and osmium (II, III or IV) can be used in the same manner. Chloroaurate (II
I), rhodium (III) chloride, potassium hexachloroiridate (IV), potassium tetrachloroylate (II
I) and potassium hexachloroosmate (IV). The inorganic or organic compound of the noble metal is not limited to the above specific examples as long as the effects of the present invention can be obtained.

The amount of adsorbed iodine (measured according to JIS K 6221) is 20 mg / g or more, preferably 30 mg / g or more, particularly preferably 50 mg / g or more, most preferably 80 mg / g or more, and dibutyl phthalate (DBP).
Oil absorption (measured by JIS K 6221) 50ml / 10
0 g or more, preferably 60 mg / 100 g or more, particularly preferably 70 ml / 100 g or more, and most preferably 10 mg / 100 g or more.
It is carbon black of 0 ml / 100 g or more. Regarding the content of hydrogen cyanide gas in the molded article, 5 ppm or less, preferably 3 ppm or less, particularly preferably 1 ppm or less.
It is preferable that the hydrogen cyanide gas scavenger be contained at most 0.5 ppm or less.

The next preferred light-shielding substance after carbon black has a refractive index of 1.5 as measured by Larsen's oil immersion method.
Zero or more inorganic pigments and various metal powders, metal flakes, metal pastes, metal fibers and carbon fibers. Representative examples of the inorganic pigment and the metal powder having a preferable refractive index of 1.50 or more are shown below, but the present invention is not limited to these. The numbers in parentheses indicate the refractive index. As the inorganic pigment having a refractive index of 1.50 or more, rutile-type titanium oxide (2.7)
5), silicon carbide (2.67), anatase type titanium oxide (2.52), zinc oxide (2.37), antimony oxide (2.35), lead white (2.09), zinc white (2. 0
2), lithopone (1.84), zircon (1.80), corundum (1.77), spinel (1.73), apatite (1.64), barite powder (1.64), barium sulfate (1 .64), magnesite (1.62), dolomite (1.59), calcium carbonate (1.58), talc (1.
58), calcium sulfate (1.56), silicic anhydride (1.
55), quartz powder (1.54), magnesium hydroxide (1.5
4), hydrochloric magnesium chloride (1.52), alumina (1.
50). Particularly preferred are those having a refractive index of 1.5.
6 or more, most preferably 1.60 or more light-shielding substances.

Calcium silicate (1.46) having a refractive index of less than 1.50, diatomaceous earth (1.45), and hydrous silicic acid (1.4)
4) and the like have a small light-shielding ability, so a large amount of addition is required, and their use as light-shielding substances is not preferred. In addition, due to the recent overseas travel boom, when a high-sensitivity photographic film having an ISO sensitivity of 400 or more is passed through an inspection machine using X-rays in baggage inspection at an airport, fog is likely to occur due to the X-rays. To prevent this, the specific gravity is 3.1 or more, preferably 3.
It is preferable to use four or more light-shielding substances. The form of the light-shielding substance having an X-ray shielding property other than the light-shielding property having a specific gravity of 3.1 or more, preferably 3.4 or more, particularly preferably 4.0 or more is not limited to those exemplified below. ,
It may be in any form, for example, pigments, powders, flakes, whiskers, fibers and the like.

As the light-shielding substance having a specific gravity of 3.1 or more,
Silicon carbide, barium sulfate, molybdenum disulfide, lead oxide (lead white), iron oxide, titanium oxide, magnesium oxide, barium titanate, copper powder, iron powder, brass powder, nickel powder, silver powder, lead powder, steel powder , Zinc powder, tungsten whisker, silicon nitride whisker, copper whisker,
Examples include iron whiskers, nickel whiskers, chromium whiskers, stainless steel powders and whiskers, magnesite, apatite, spinel, corundum, zircon, antimony trioxide, barium carbonate, zinc white, chromium oxide, tin powder, and mixtures thereof.

Particularly preferred light-shielding substances for imparting X-ray shielding properties include zircon, corundum, barium sulfate, barium chloride, barium titanate, lead powder, lead oxide, zinc powder, zinc white, tin powder, and stainless steel powder. , Stainless whisker, iron oxide, tungsten whisker, nickel whisker. A light-shielding substance particularly preferable as a molded article for an ultrahigh-sensitivity photographic light-sensitive material having an ISO sensitivity of 400 or more has a refractive index of 1.50 or more and a specific gravity of 3.1 or more, and most preferably has a refractive index of 1.56 or more. , A light-shielding substance having a specific gravity of 3.4 or more. The content of these light-shielding substances varies depending on the layer thickness and the type and application of the resin, but the physical strength,
It is 0.1 to 80% by weight, preferably 0.3 to 60% by weight, more preferably 0.5 to 40% by weight, most preferably 1.0 to 20% by weight from the viewpoint of economy, production suitability and the like.

Table 1 shows the refractive index and specific gravity of the light-shielding substance.

[0141]

[Table 1]

The content of the X-ray shielding light-shielding substance is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, and most preferably 20 to 60% by weight. 5% by weight
When the amount is less than the above, there is almost no X-ray blocking effect, and when the amount exceeds 80% by weight, the production is difficult, and the physical strength and the heat sealing property are lacking, so that it is difficult to put to practical use.

The above-mentioned various light-shielding substances preferably have a loss on drying at 100 ° C. for 5 hours of not more than 2.0% by weight so as not to adversely affect the photographic light-sensitive material and to deteriorate the film formability. More preferably 1.0% by weight or less,
Most preferably, it is used in a state of 0.5% by weight or less.

The present invention improves the photographic properties of a photographic light-sensitive material having an effect of adsorbing a lubricant, an antioxidant or an organic nucleating agent, which is easy to bleed out, and adsorbing a deodorant, an aromatic agent, an oxygen scavenger and the like. Representative examples of oil-absorbing inorganic pigments preferably contained in the present invention include zinc white (52), asbestin (50), clay (51), titanium oxide (56), kaolin (60), talc (60), and carbon black. (60 or more) and activated carbon. The number in parentheses is the oil absorption (measured by the oil absorption A method of JIS K 6221. Unit: ml)
/ 100g).

Representative examples of metal powder (including metal paste) include aluminum powder, aluminum paste, copper powder, stainless steel powder, iron powder, nickel powder, brass powder, silver powder, tin powder, zinc powder, steel powder and the like. There is.

The term “aluminum powder” as used in the present invention includes both aluminum powder and aluminum paste. A powder obtained by coating the surface of an aluminum powder with a surface coating substance and a powder obtained by removing a low-volatile substance from the aluminum paste are treated with a thermoplastic resin. What is kneaded is preferable. The average particle size is 0.3 to 50 μm to make aluminum powder excellent in uniform dispersibility, moldability, photographic properties, appearance and low odor.
m, preferably 0.5 to 45 μm, particularly preferably 0.
8 to 40 μm, average thickness of 0.03 to 0.5 μm, preferably 0.05 to 0.4 μm, particularly preferably 0.08 to
It is an aluminum powder having 0.35 μm and a fatty acid content of 5% by weight or less, preferably 4% by weight or less, particularly preferably 3% by weight or less.

Here, the aluminum paste refers to the presence of mineral spirit and a small amount of higher fatty acids such as stearic acid or oleic acid when aluminum powder is prepared by a known method such as ball milling, stamp milling or atomizing. Originally made in paste form. In the present invention, this aluminum paste and various aromatic monovinyl resins (polystyrene resin, rubber-containing polystyrene resin, etc.), and polyolefin thermoplastic resins (various polypropylene resins, various polyethylene resins, acid-modified resins, EVE resins, EEA resins, EAA resins, etc.) , Low molecular weight polyolefin resin, paraffin wax, tackifier, dispersing agent such as metal soap, etc. by heating and kneading, low volatile substances (mainly mineral spirits and white spirits with strong odor)
Was removed by a vacuum pump or the like.
3% or less, preferably 1%
Hereinafter, it is particularly preferable to use one having 0.5% or less as an aluminum paste compound resin or an aluminum paste masterbatch resin.

It is particularly preferable to use the resin as an aluminum paste masterbatch resin in order to eliminate adverse effects and odors on the photographic material. For example, even if the mineral spirit content in a masterbatch resin having an aluminum paste content of 40% by weight is 1.0% by weight, the content of the aluminum paste in a molded product for a photographic material is reduced to 2%.
If it is attempted to make the weight percentage, 19 parts by weight of the natural resin is kneaded with respect to 1 part by weight of the aluminum paste master batch, and some of the packaging material may remove mineral spirit as a gas by heating during molding. Therefore, the mineral spirit content becomes 0.05% by weight or less. As a result, there is no adverse effect on the photographic light-sensitive material, and the odor is reduced.

The aluminum powder is obtained by pulverizing molten aluminum into powder by an atomizing method, a granulating method, a rotating disk dropping method, an evaporation method, or the like, and crushing aluminum foil by a ball mill method, a stamp mill method, or the like. Including Since aluminum powder alone is unstable, various known surface coating treatments for inactivating the aluminum powder surface are performed. In particular, a specific thickness (5-20 μm,
Preferably 6 to 15 μm, particularly preferably 7 to 10 μm
m), the aluminum foil rolled in step m) is cut with a shredder or the like, annealed and fatty acids are removed, and then 5% by weight or less of fatty acids having 8 or more carbon atoms (including compounds) in the cut aluminum foil. And an average particle size of 0.3 to 5 using at least one of a pulverizer selected from a ball mill, a stamp mill, a vibration mill and an attritor.
Aluminum powder having a thickness of 0 μm, an average thickness of 0.03 to 0.5 μm, and a fatty acid content of 5% by weight or less is particularly preferred in the present invention because of its excellent dispersibility, photographic properties, and low gloss.

For practical use as a molded product for a photographic light-sensitive material of the present invention, it is necessary to ensure quality, physical strength, photographic performance,
From the viewpoint of moldability and economy, the total content of the light-shielding substance is 0.1%.
The content is 1 to 80% by weight, but the content varies depending on the light-shielding ability and the average particle diameter of the light-shielding substance. In the case of carbon black, titanium oxide and aluminum powder having excellent light-shielding ability, the total content in the light-shielding layer is from 0.1 to 60% by weight, from 0.3 to 60% in view of light-shielding properties, economy, film formability and the like. 40
% By weight, more preferably 0.5 to 20% by weight, most preferably 1 to 10% by weight. When the content is less than 0.1% by weight, unless the thickness of the molded article for photographic light-sensitive material (in the case of a film-shaped molded article) is increased, the light-shielding ability becomes insufficient and light fog occurs. For this reason, the molding speed of the molded article for photographic light-sensitive materials becomes slow (because the cooling time becomes long),
Because of the large amount of resin used, it becomes expensive and is difficult to put into practical use. If the content exceeds 60% by weight, the cost becomes high, the dispersibility deteriorates, the generation of microgrids (aggregated impurities) increases, pressure fog and abrasion occur on the photographic material, and molding for the photographic material is performed. The amount of water in the product increases due to an increase in the amount of water adsorbed on the carbon black, and adversely affects the photographic performance of the photographic light-sensitive material (fog generation, abnormal sensitivity, abnormal coloring, etc.). Further, the moldability of molded articles for photographic light-sensitive materials is deteriorated (foaming, silver stripes, pinholes, breakage, etc.) and the physical strength is reduced, which makes practical use difficult.

Resin of light-shielding substance (carbon black, aluminum powder, inorganic pigment having a refractive index of 1.50 or more, inorganic pigment having a specific gravity of 3.4 or more, and inorganic pigment having an oil absorption of 50 ml / 100 g or more are particularly preferable) Improvement of dispersibility in the inside, improvement of resin fluidity, prevention of generation of micro grit that generates friction fog, pressure fog, abrasion, etc. on photographic photosensitive materials, prevention of generation of volatile substances harmful to photographic properties, reduction of moisture absorption, It is preferable to coat the surface with a surface coating material to prevent die lip contamination.

Representative examples of the surface coating substance are shown below. (1) Coupling agent Coupling agent coating containing azidosilanes
Silane-based coupling agent coating (aminosilane, etc.) titanate-based coupling agent coating (2) silica is deposited, followed by alumina deposition coating (3) zinc stearate, magnesium stearate,
Higher fatty acid metal salt coating such as calcium stearate (4) Surfactant coating such as sodium stearate, potassium stearate, oxyethylene dodecyl amine (5) Barium sulfide aqueous solution and sulfuric acid aqueous solution in the presence of excess barium ion With an average particle diameter of 0.1 to
An aqueous solution of alkali silicate is added to the water slurry to form barium silicate on the surface of barium sulfate, and then mineral acid is added to the slurry to decompose the barium silicate to hydrated silica. (6) Metal hydrated oxide (one or more hydrated oxides of titanium, aluminum, cerium, zinc, iron, cobalt or silicon) and / or metal oxide (One or two or more oxides of titanium, aluminum, cerium, zinc, iron, cobalt or silicon) Surface coated with a composition consisting only of (7) Aziridine group, oxazoline group and N-
Coated with a polymer having one or more reactive groups selected from the group consisting of hydroxyalkylamide groups (8) coated with a polyoxyalkyleneamine compound (9) cerium cation, selected acid anion and alumina (10) Surface coated with an alkoxytitanium derivative having an α-hydroxycarboxylic acid residue as a substituent (11) Surface coated with polytetrafluoroethylene (12) Surface coated with polydimethylsiloxane or modified silicone (13) (14) Surface coating with 2- to 4-hydric alcohol (15) Surface coating with olefin wax (polyethylene wax, polypropylene wax) (16) Surface coating with hydrous aluminum oxide (17) Silica or zinc compound ( Zinc chloride, zinc hydroxide,
(18) Surface coating with polyhydroxy saturated hydrocarbon (19) Surfactant (cationic type) (18) Surface coating with zinc oxide, zinc sulfate, zinc nitrate, zinc acetate, zinc acetate, zinc citrate, etc.) (20) Organometal chelate compounds (especially β-diketone chelate compounds are preferred because they are excellent in photographic properties and dispersibility, etc.) The surface coating amount is 100 parts by weight of a light-shielding substance (Preferably 0.001 to 20 parts by weight, preferably 0.01 to 15 parts by weight) and a surface coating (21) an aliphatic monocarboxylic acid having 20 to 40 carbon atoms and an aliphatic monocarboxylic acid having 20 to 40 carbon atoms. (22) Surface coating with metal salt of partially saponified fatty acid ester having 20 to 50 carbon atoms, etc.

As the surface coating material of the light-shielding material, there is little adverse effect such as fogging on the photographic characteristics of the photographic light-sensitive material.
(1), (3), (12), (14), (1)
In addition to 5), (16), (18), (19), (21), and (22), organometal chelate compounds, various antistatic agents, lubricants, and drip-proof agents are preferable.

In particular, an ester of an aliphatic monocarboxylic acid having 20 to 40 carbon atoms and an aliphatic monohydric alcohol having 20 to 40 carbon atoms is used in an amount of 0.0 to 100 parts by weight of the light-shielding substance.
It has been found that the effect of preventing the above problems can be exhibited by adding 0.01 to 20 parts by weight, preferably 0.005 to 10 parts by weight, particularly preferably 0.01 to 5 parts by weight. In particular, it not only reduces the adverse effect on the photographic properties of the photographic light-sensitive material but also reduces the motor load, improves the dispersibility of the light-shielding substance, improves the moldability, and improves the appearance of the molded article.

The ester used in the present invention includes an aliphatic monocarboxylic acid having 20 to 40 carbon atoms, preferably 25 to 35 carbon atoms, and an aliphatic monocarboxylic acid having 20 to 40 carbon atoms, preferably 25 to 3 carbon atoms.
5 is an ester of an aliphatic monohydric alcohol.

Examples of the above-mentioned monocarboxylic acids include montanic acid, melicic acid, cerotic acid, bricinic acid, lacceric acid and the like.

Examples of the monohydric alcohol include montyl alcohol, merisyl alcohol, lacsyl alcohol,
Seryl alcohol, brisyl alcohol and the like can be mentioned.

[0158] Since these improve the fluidity of the thermoplastic resin and achieve uniform kneading, they are very excellent as a surface coating material of the light shielding material. further,
When used as a dispersant for the inorganic and / or organic nucleating agent in the surface coating, various excellent effects such as scattering prevention, bleed-out prevention, uniform dispersibility improvement, and resin fluidity improvement are exhibited.
The surface coating amount of the light-shielding substance is 0.001 to 20 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the light-shielding substance such as carbon black, titanium oxide or aluminum powder. Parts by weight, more preferably 0.01 to 3 parts by weight, most preferably 0.05 to 1.
5 parts by weight. When the coating amount is 0.001 part by weight or less, the coating effect is hardly exhibited. If the coating amount exceeds 20 parts by weight, the occurrence of bleed-out increases with time.

The total sulfur content (AST) in the above total light-shielding substance
MD-1619) is at most 0.9%, preferably at most 0.7%, particularly preferably at most 0.5%, and the free sulfur content is at most 150 ppm, preferably at most 50 ppm, particularly preferably at most 30 ppm. , ASTM D-150
6, the ash content is 0.5% or less, preferably 0.4% or less, particularly preferably 0.3% or less, and the aldehyde compound content is 0.2% or less, preferably 0.1% or less;
It is particularly necessary to take care that if the content is not less than 0.05%, the photographic properties will be adversely affected.

Further, a cyanide compound also adversely affects the photographic performance of a photographic light-sensitive material.
The value obtained by converting the amount of hydrogen cyanide quantified by pyrazolone absorption spectrometry into ppm unit based on the weight of the light-shielding substance is 20.
A light-shielding substance of at most 10 ppm, preferably at most 10 ppm, particularly preferably at most 5 ppm, most preferably at most 1 ppm is used.

A nucleating agent (an organic nucleating agent and an inorganic nucleating agent) can be contained in the resin composition of the molded article for a photographic light-sensitive material of the present invention. By including a nucleating agent, crystallization speed, molding cycle shortening, rigidity improvement, transparency and deformation prevention, molding failure reduction, physical strength improvement, and the like can be achieved.

The nucleating agent is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1.7 parts by weight, more preferably 0.05 to 100 parts by weight of the thermoplastic resin.
To 1.4 parts by weight, particularly preferably 0.07 to 1 part by weight,
Most preferably, 0.10 to 0.6 parts by weight is blended.

When the amount of the nucleating agent is less than 0.01 part by weight, there is no compounding effect and the cost is merely increased. When the amount exceeds 2 parts by weight, the effect of increasing the amount is not obtained and smoke and off-flavor increase. Photographic properties are adversely affected, and bleed-out is increased to generate white powder.

Organic nucleating agents include carboxylic acids, dicarboxylic acids, salts and anhydrides thereof, salts and esters of aromatic sulfonic acids, aromatic phosphinic acids, aromatic phosphonic acids, aromatic carboxylic acids, aluminum salts thereof, Metal salts of aromatic phosphates, alkyl alcohols having 8 to 30 carbon atoms, condensates of polyhydric alcohols and aldehydes, and alkylamines, such as aluminum pt-butyl benzoate, 1,3,2,4 dibenzylidene Sorbitol, di-substituted benzylidene sorbitol compounds, metal salts of stearyl lactic acid such as calcium and magnesium, N- (2-hydroxyethyl) -stearylamine, lithium salts of 1.2 hydroxystearic acid, sodium salts and potassium salts,
Metal salts such as calcium salts and magnesium salts, alkyl alcohols such as stearyl alcohol and lauryl alcohol, sodium benzoate, benzoic acid, sebacic acid and the like are included.

Examples of the organic nucleating agent that can be used in the present invention include:
Carboxylic acids, dicarboxylic acids, salts and anhydrides thereof, salts and esters of aromatic sulfonic acids, aromatic phosphinic acids, aromatic phosphonic acids, aromatic carboxylic acids, other aluminum salts, metal salts of aromatic phosphates, carbon Examples include alkyl alcohols of Formulas 8 to 30, condensates of polyhydric alcohols and aldehydes, and alkylamines.
-Butyl aluminum benzoate, 1,2,3,4-dibenzylidene sorbitol, disubstituted benzylidene sorbitol compound represented by the following formula

[0166]

Embedded image In the formula, R ₁ and R ₂ are alkyl, alkoxy or halogen having 1 to 8 carbon atoms, m and n are each 0 to 3 and m + n ≧ 1.化合物, metal salts of stearyl lactic acid such as calcium and magnesium, and compounds represented by the following formulas such as N- (2-hydroxyethyl) -stearylamine.

[0167]

Embedded image Wherein R ₃ is an alkyl group having 8 to 30 carbon atoms;
k and 1 are both 0 to 10 and k + 1 ≧ 1. ｝, Metal salts such as lithium, sodium, potassium, calcium and magnesium salts of 1,2-hydroxystearic acid, alkyl alcohols such as stearyl alcohol and lauryl alcohol, sodium benzoate,
Examples include benzoic acid and sebacic acid.

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

By incorporating the above-mentioned dibenzylidene sorbitol compound into the resin composition of the present invention, it is possible to obtain physical strength, rigidity, bleed-out resistance, odorlessness, transparency, photographic properties, moldability, abrasion resistance and the like. An excellent molded article for a photographic light-sensitive material can be provided.

Although the reason why the preferred organic nucleating agent of the present invention exhibits the above-mentioned excellent effects is not necessarily clear, it is not obvious that the conventional raw materials for producing dibenzylidene sorbitol, benzaldehyde, and p, which is the raw material for producing the above-mentioned dibenzylidene sorbitol derivative. A benzaldehyde derivative such as a substituted benzaldehyde has an odor, and both of them inevitably remain in dibenzylidene sorbitol (derivative) even after purification, causing an unpleasant odor of the molded article for a photographic light-sensitive material of the present invention. It is conceivable that the benzylidene sorbitol compound is slightly decomposed by heating during molding to generate an aldehyde compound, which causes an unpleasant odor.

The various organic nucleating agents may be used alone or in combination with various inorganic nucleating agents or in combination of two or more organic nucleating agents. In addition, the surface of the organic and inorganic nucleating agent may be various fatty acids, lubricants such as fatty acid compounds and silicones, coupling agents, plasticizers, dispersants such as surfactants and wetting agents, and surface coating materials of the light-shielding material. It can be coated with (1) to (20). Particularly preferred are dibenzylidene sorbitol compounds whose surface is coated with one or more of higher fatty acids, higher fatty acid compounds (preferably higher fatty acid metal salts) and a plasticizer.

Of the organic nucleating agents, the following dibenzylidene sorbitol compounds are particularly preferred. In particular, improvement of Young's modulus, improvement of physical strength, improvement of rigidity, improvement of hardness, improvement of abrasion resistance, improvement of dimensional accuracy, improvement of crystallization speed of polyethylene resin,
The following di-substituted benzylidene sorbitol compositions capable of exhibiting effects such as improvement of molding speed, reduction of molding failure and the like, and improvement of odor and bleed-out which are disadvantages of conventional organic nucleating agents are particularly preferred.

As an essential component of the di-substituted benzylidene sorbitol composition, a compound represented by the general formula (I)

Embedded image Wherein R and R ′ are each independently a chlorine atom,
A solid powder of a dibenzylidenesorbitol derivative of formula (II) which represents an atom or group selected from the group consisting of a methyl group and an ethyl group;

CH ₃ (CH ₂ ) _n COOH (II) wherein n is a number from 14 to 30, preferably from 18 to 27, most preferably from 20 to 25. A dibenzylidene sorbitol derivative composition comprising the higher fatty acid covering the surface of a solid powder of the dibenzylidene sorbitol derivative is contained.

The dibenzylidene sorbitol derivatives of the general formula (I) preferably used in the present invention include 1,3-
2,4-di-p-methylbenzylidene sorbitol, 1,3-
2,4-di-p-ethylbenzylidene sorbitol, 1,3-
p-Methylbenzylidene-2,4-p-chlorobenzylidenesorbitol, 1,3-p-methylbenzylidene-2,4-
Examples thereof include p-ethylbenzylidene sorbitol and 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol.

In a preferred embodiment of the organic nucleating agent of the present invention, in the general formula (I), a dibenzylidene sorbitol derivative in which R and R ′ each independently represent a methyl group or a chlorine atom is used.

Particularly preferred dibenzylidene sorbitol derivatives are 1,3-2,4-di-p-methylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p
Chlorobenzylidene sorbitol and 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol.

Preferred examples of the higher fatty acids of the formula (II) which are preferably used as organic nucleating agents in the present invention are behenic acid, stearic acid and palmitic acid, among which behenic acid is most preferred and stearic acid is preferred. Next.

The particle size of the solid powder of the dibenzylidene derivative used in the organic nucleating agent composition of the present invention is not particularly limited, and a particle size distribution of 30 to 100 mesh is preferably used.

The preferred organic nucleating agent composition of the present invention comprises 95 to 50 parts by weight, preferably 9 parts by weight of the dibenzylidene derivative.
5 to 50 parts by weight, preferably 10 to 5 parts by weight of 0 to 50 parts by weight of at least one of higher fatty acids and / or higher fatty acid compounds (such as fatty acid metal salts and fatty acid amides) and / or plasticizers.
In a range of 0 parts by weight, the total content of both components is 100 parts by weight.

A particularly preferred organic nucleating agent composition according to the present invention is an aqueous emulsion containing the above-mentioned ratio of higher fatty acid and / or one or more of higher fatty acid compounds and / or plasticizers in an aqueous emulsion containing the above-mentioned ratio of dibenzylidene sorbitol derivative. The solid powder is added and stirred to form at least one coating layer of a higher fatty acid and / or a higher fatty acid compound and / or a plasticizer on the surface of the solid powder of the dibenzylidene sorbitol derivative. The dibenzylidene sorbitol derivative powder having at least one coating layer of a compound and / or a plasticizer can be prepared by filtration, followed by washing and drying.

The aqueous emulsion of higher fatty acid, higher fatty acid compound or plasticizer used in the above method may be, for example, a concentration of at least one of higher fatty acid, higher fatty acid compound and plasticizer of 5 to 50% by weight, preferably 10 to 50% by weight. weight%
A small amount of a surfactant, for example, 1 to 10 parts by weight, preferably 2 to 5 parts by weight, of at least one kind of higher fatty acid, higher fatty acid compound and plasticizer per 100 parts by weight. It can be easily obtained by dispersing in water.

The presence of at least one coating layer of a higher fatty acid, a higher fatty acid compound and a plasticizer formed on the surface of the solid powder of the dibenzylidene sorbitol derivative is observed by dyeing the coating layer with a dye. Can be confirmed by In addition, it is also preferable to coat the surface of the organic nucleating agent with a surface coating material of a light-shielding material described below from the viewpoint of improving dispersibility.

The preferred organic nucleating agent composition of the present invention comprises
Examples of the polyolefin-based resin which is effectively used as an additive for improving physical strength, non-bleed-out property and odorless property include an aliphatic monoolefin having 2 to 6 carbon atoms having a number average molecular weight of 10,000. ~ 600,000, preferably 11,000 to 500,000, particularly preferably 12,000.
000 to 400,000, most preferably 13,000
-300,000 high molecular weight homopolymer or copolymer, for example, low density homopolyethylene resin, high density homopolyethylene resin, linear polyethylene (ethylene-α-
(Olefin copolymer) resin.

In the preferred organic nucleating agent composition of the present invention, it is important that the surface of the solid particles of the dibenzylidene sorbitol derivative is coated with at least one of a higher fatty acid, a higher fatty acid compound and a plasticizer. Dibenzylidene sorbitol derivatives and higher fatty acids in the resin,
Even if one or more of the higher fatty acid compound and the plasticizer are simply added and mixed, the above-mentioned sufficient effects cannot be achieved. Also, 1
The sufficient effect described above cannot be achieved unless the heat history of 80 ° C. or more, preferably 190 ° C. or more, particularly preferably 200 ° C. or more is passed once or more.

The preferred organic nucleating agent composition of the present invention, when blended with a polyolefin resin composition, does not impair any of the properties such as physical strength, bleed-out resistance and rigidity as compared with the prior art. Depending on the case, these characteristics are further improved, and at the same time, excellent odorlessness is obtained, and excellent effects such as reduction of molding failure such as gate residue are exhibited. That is, by including the di-substituted benzylidene sorbitol composition in the polyethylene resin composition of the present invention, physical strength, rigidity, bleed-out resistance, odorlessness, film moldability, injection moldability, dimensional accuracy, It is possible to provide a container body for a photographic film cartridge excellent in abrasion resistance and the like.

Although the reason why the preferred organic nucleating agent composition of the present invention exhibits the above-mentioned excellent effects is not necessarily clear,
Benzaldehyde, a conventional raw material for producing dibenzylidene sorbitol, and a benzaldehyde derivative such as p-substituted benzaldehyde, which is a raw material for producing the dibenzylidene sorbitol derivative of the present invention, have an odor, and both of them are inevitable even after purification. ), Which tends to cause a bad odor in transparent or light-shielding injection-molded products or transparent or light-shielding thermoplastic resin films, etc., and a thermoplastic resin in which dibenzylidene sorbitol (derivative) is used as a thermoplastic resin composition. It is conceivable that some decomposition may occur during injection molding, thermoplastic resin film molding, and the like, causing an unpleasant odor.

In a preferred organic nucleating agent composition of the present invention, solid particles of a specific dibenzylidene sorbitol derivative of the general formula (I) are used, and the particles are coated with a specific higher fatty acid of the general formula (II). By simultaneously satisfying the requirements of, for example, the unpleasant odor presumed to be based on the raw material benzaldehydes or decomposed benzaldehydes, using a thermoplastic resin composition, a thermoplastic resin injection molded article or a thermoplastic resin film Etc., and rigidity, hardness, dimensional accuracy, wear resistance,
The effect that the various physical properties such as the physical strength are also excellent is also exhibited.

The various organic nucleating agents can be used alone or in combination with various inorganic nucleating agents or in combination of two or more organic nucleating agents. In addition, the surface of the organic and inorganic nucleating agents can be coated with various fatty acids, fatty acid compounds, silicones and other lubricants, coupling agents, plasticizers, dispersants such as surfactants, wetting agents, and the like.

One or more of a conductive substance and an antistatic agent can be added to the molded article for a photographic light-sensitive material of the present invention. The addition of one or more conductive substances or antistatic agents prevents or suppresses the generation of static electricity caused by friction between the photographic photosensitive material and a molded product when handling the photographic photosensitive material. Prevent the generation of static marks.

The total content of one or more of the conductive substance and the antistatic agent is preferably 0.01 to 40% by weight.
0.03 to 30% by weight is more preferable, and 0.05 to 20% by weight is most preferable. If the total content is less than 0.01% by weight, there is no effect of addition and only the cost of kneading is increased. On the other hand, if the total content exceeds 40% by weight, there is no effect of increasing the amount and the cost is merely increased. In the case of an antistatic agent, the occurrence of slip with the screw of the extruder increases, so that a uniform amount of resin cannot be supplied, and molding failure frequently occurs. Further, the amount of bleed-out increases with time, and the surface of the molded article becomes sticky and reduces the commercial value.

The conductive material has an average particle size of 12 to 50.
mμ, various carbon blacks having a DBP oil absorption of 100 ml / 100 g or more, specifically, various conductive carbon blacks (for example, conductive furnace black Continex CF, Parcan C, etc., superconductive furnace black Continex SC, etc.)
F, Vulcan SC, etc. Asahi HS-500 and Vulcan XC-72 with extra conductive furnace black
, Conductive Channel Black Colux L, etc., Mitsubishi Conductive Carbon Black # made by Mitsubishi Kasei KK
3050, # 3150, # 3250, # 3600, # 3
750, # 3950, etc.), acetylene carbon black
(Electrified acetylene black, Shaunigan acetylene black, etc.), Ketjen carbon black (EC and EC
-600 JD, etc.), carbon fiber, metal fiber, Al-doped,
TiO 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.

Among the above antistatic agents, non-ionic (nonionic) antistatic agents (=) have a small adverse effect on photographic properties and human body and a large effect of preventing static mark generation.
Surfactants) are particularly preferred.

In addition, "Handbook: Rubber / Plastic Compounding Chemicals Revised Second Edition" (published by KK Rubber Digest)
Pp. 381-388 and "Augmented Antistatic Agents-Surface Modification of Polymers" (published on March 25, 1972, KK Koshobo), pp. 64-104 and 236-.
From the antistatic agent described on page 266 and the antistatic agent described on pages 117 to 153 of "Sekkabun Kogyo Kogyo Kogyo Plastic Additives Data Book" (published on October 1, 1968 by KK Kagaku Kogyo Co., Ltd.) to photographic photosensitive materials It is preferable to select and use a kind and an addition amount which do not adversely affect a molded article made of a thermoplastic resin which easily generates a static mark on a photographic material by charging.

Representative examples of molded articles for photographic light-sensitive materials of the present invention are shown below, but the present invention is not limited to these.

(1) Film-formed product Single-layer film-formed product (FIG. 1);
Publication etc. Multi-layer co-extruded film molded products (FIGS. 2, 3, 4,
FIG. 5); a laminated film using a single-layer film molded product or a multilayer co-extruded film molded product (FIGS. 6, 7, and 8); Japanese Patent Publication No. 63-26697, Japanese Patent Publication No. 2-2701;
JP-B-2-13774, JP-B-2-19225, etc. Packaging materials using the above flexible sheets; packaging bags (unipack bags, single flat bags, double flat bags, single gusset bags, double Gusset bag etc.), shring package, bulk package (Japanese Patent Laid-Open No. 3-53243,
No. 71346, etc.) Collective packaging and the like, and a package for loading a belt-shaped photosensitive material into a light room Japanese Utility Model Publication No. 55-113543, Japanese Utility Model Application Laid-open No. 60-133
No. 86, Japanese Utility Model Application Laid-Open No. 60-167796, Japanese Utility Model Application Laid-Open No. 3-47547, Japanese Utility Model Application Laid-Open No. 3-54937,
JP-A-3-86358, JP-A-3-96648, JP-A-2-72347, etc.

(2) Injection molded product Photographic film cartridge, photographic film spool, photographic film unit with lens, photographic film cartridge, light-shielding container, resin photographic film cartridge, sheet or roll photographic photosensitive material Light-shielding magazine for loading materials into light rooms, cores, cartridges for photographic films, packs for instant photographic films, holders for sheet-like photographic films, cameras for photographic film photography, packs for cut films, photographic photosensitive material processing machines, etc.

1. Photographic disc film cartridge; Japanese Utility Model Publication No. Sho 60-21743

2. Film unit with lens;
JP-A-3-226543, JP-A-3-129341, JP-A-6-11798, JP-A-7-2951
No. 50, Japanese Patent Application Laid-Open No. Hei 10-62910, Japanese Utility Model 5
No. 2,919, JP-B-2-32615, U.S. Pat. No. 5,773,205, etc.

[0200] 3. Spool for photographic film;
-120931, JP-A-58-178139-1
78145, JP-A-63-73742, JP-A-57-196218, JP-A-58-8223.
No. 6, JP-A-58-82237 and JP-A-58-82237.
-203436, JP-A-59-15049, JP-A-62-240957, and JP-A-3-12.
9341, JP-A-4-33538, JP-A-7-295150, JP-A-9-319034, JP-A-10-83044, and JP-B-44-1.
No. 6,777, JP-B-55-31541, U.S. Pat. No. 1,930,144, and British Patent No. 2,1998.
05A specification etc.

4. Patrone for photographic film made of resin; Japanese Utility Model Laid-Open No. 55-97738, JP-A-50-33831
JP-A-5-111822 and JP-A-56-112822
-87039, JP-A-57-190948, JP-A-1-251030, JP-A-1-312
538, JP-A-2-181141, JP-A-2-221965, JP-A-3-116136, JP-A-3-129341, JP-A-4-378
44, JP-A-4-115251, JP-A-4-115251
-273240, JP-A-4-320258, JP-A-4-335344, JP-A-4-335
639, JP-A-4-343353, JP-A-4-349454, JP-A-7-295150, JP-A-9-319037, JP-A-9-329
869, JP-A-10-62908, JP-A-10-62910, JP-A-10-83042, JP-A-10-123668, JP-A-10-1
23669, JP-B-45-6991, JP-B-55-21089, U.S. Pat. No. 4,846,4
No. 18, U.S. Pat. No. 4,848,693, U.S. Pat. No. 4,887,776

5. Containers for photographic film cartridges: Japanese Utility Model Application Laid-Open No. Sho 60-163451, Japanese Utility Model Application Laid-Open No. 1-88940, Japanese Utility Model Application Laid-Open No. 1-113235, Japanese Utility Model Application Laid-open No. 1-15
2337, JP-A-61-73947, JP-A-61-250639, and JP-A-62-29163.
No. 9, JP-A-63-121047, JP-A-Hei 2
JP-A-214855, JP-A-2-247640, JP-A-3-91741, JP-A-3-1293
No. 41, JP-A-6-19054, JP-A-10
-62912, JP-A-2-33236, JP-A-3-48581, JP-B-2-38939, U.S. Pat. No. 4,801,011, U.S. Pat. No. 4,639,386. The specification, U.S. Pat.
No. 351, European Patent No. 0237062A2, European Patent No. 0280065A1, European Patent No. 0298375A2, etc.

6. Core and reel;
No. 48, U.S. Pat. No. 4,809,923, British Patent No. 2033873.

7. Magazine for sheet photographic film; JP-A-56-5141

8. Photographic film cartridge; Japanese Utility Model Laid-Open No. 2-24646, Japanese Utility Model Laid-Open No. 2-29041,
Japanese Patent Application Laid-Open No. Hei 1-312537, and Japanese Utility Model Publication No. 56-1661.
No. 0, Japanese Utility Model Publication No. 60-120448, etc.

9. Photographic film case;
No. 100617, Japanese Utility Model Publication No. 64-32343,
JP-A-1-94258, JP-A-2-56139, JP-B-2-54934, U.S. Pat.
79,756, EP 0 242 905 A1
Issue specifications, etc.

10. Instant film pack: Japanese Utility Model Application Laid-Open No. 61-41248, JP-A-62-240961
No.

11. Packs and holders for sheet photographic films: JP-A-4-238331, JP-A-4-24
7440, JP-A-4-335334, JP-A-4-349449, JP-A-4-350634, JP-A-5-341378, JP-A-5-34
1379, JP-A-5-341380, JP-A-5-341381, JP-A-6-75291, JP-A-6-75292, JP-A-6-7529
3, JP-A-8-110568 and JP-A-8-110568.
No. 201983, Japanese Unexamined Patent Publication No. Hei 8-201984,
JP-A-9-179248, JP-A-10-1047
No. 37, JP-A-10-104801, JP-T-4-504014, U.S. Pat. No. 4,725,865.
No., U.S. Pat. No. 4,821,055, etc.

A method for forming a molded article for a photographic light-sensitive material is as follows.
A known method may be used depending on the form of each molded product. For example, blown film molding, extrusion lamination molding, injection molding, gas assist molding, blow molding (blow molding), combined injection and blow molding, vacuum molding, and vacuum pressure molding , Press molding, sheet molding, T-die flat film molding, air pressure molding, rotational molding, vacuum injection molding in a mold, and the like.

The photographic light-sensitive material package of the present invention is obtained by molding a molded product for a photographic light-sensitive material as described above to which the photographic light-sensitive material is applied, with a moisture permeability of 10 g / m ^2. The package is sealed with a moisture-proof packaging material of not more than time, preferably 7 g / m ² · 24 hours or less, more preferably 5 g / m ² · 24 hours or less, particularly preferably 3 g / m ² · 24 hours or less, most preferably Preferably, it is sealed and packaged with a moisture-proof packaging material of 1 g / m ² · 24 hours or less.

If the moisture permeability exceeds 10 g / m ² · 24 hours, the photographic properties of the photographic material containing a large number of sensitizing dyes, couplers, antihalation dyes, various additives, etc., which are degraded by moisture, will be extended for a long time (6 hours). Cannot be kept in good condition. Further, in a photographic light-sensitive material in which a gelatin layer which easily blocks when moisture is absorbed is present on one or both of the front and back surfaces of the support, blocking is liable to occur, and practical use is difficult.

Further, the oxygen permeability of the moisture-proof packaging material (JIS
K-7126 at 20 ° C., 0% RH)
cc / m ² · 24 hours · 1 atm or less, preferably 500
cc / m ² · 24 hours · 1 atm or less, particularly preferably 1
00 cc / m ² · 24 hours · 1 atm or less, most preferably 50 cc / m ² · 24 hours · 1 atm or less. When the oxygen permeability exceeds 1000 cc / m ² · 24 hours · 1 atm, sensitizing dyes degraded by oxygen, antihalation dyes, couplers and other additives in the emulsion coating layer of photographic materials which are easily oxidized deteriorate. As a result, the photographic properties are deteriorated, and it is difficult to put it to practical use. In particular, color photographic photosensitive materials that require color balance (negative film, positive film,
Printing paper, reversal film, auto-positive film, instant film, etc.) cannot be put to practical use.

Examples of the moisture-proof packaging material include a single-layer thermoplastic resin film for packaging bags, shrink packaging and overlap packaging, various flexible sheets (various papers (wood pulp paper, non-wood pulp paper, coated paper, Printed paper, etc.), synthetic paper, cellophane, metal foil, thermoplastic resin film, metal or inorganic oxide vapor-deposited film, metal or inorganic oxide vapor-deposited paper, etc.) laminated via an adhesive layer or via an adhesive layer. And a multilayer film in which a plurality of thermoplastic resin films are co-extruded simultaneously and a multilayer film in which inner layers of a multilayer co-extrusion blown film are adhered by blocking.

The thermoplastic resin film includes various resin films which have been subjected to processing such as non-stretching, uniaxial stretching and biaxial stretching. As a thermoplastic resin film, ultraviolet cut, biodegradable, photodegradable, antibacterial, aromatic, odor absorbing, antifogging, etc.
Also includes films with special functions. A particularly preferred moisture-proof packaging material is a laminated film obtained by laminating at least one of a metal foil and a metal or inorganic oxide-deposited thermoplastic resin film, and most preferably a biaxially stretched thermoplastic resin film on which a metal or inorganic oxide is deposited. It is.

Representative examples of commercially available metal or inorganic oxide vapor deposited thermoplastic resin films are shown below. Evaporated film (metal-deposited thermoplastic resin film) Oike Kogyo Co., Ltd .: Evaporated film “Oike no Evaporated Film” Ruitsu: Evaporated film “Ruitsu Evaporated Film” Tosero Co., Ltd .: Evaporated film “Tocello” Metaline (M
L) Film "Toyobo Co., Ltd .: Evaporated film" Toyobo Evaporated Film "Toyo Metallizing Co., Ltd .: Evaporated film" Toyo Metallized Evaporated Film "Nakai Kogyo Co., Ltd .: Evaporated polyester film" Nakai High Reflective Film Silver) "Nakai Kogyo Co., Ltd .: Evaporation film" Nakai evaporation film "Nippon Koban Co., Ltd .: Evaporation film" Koban metallic film Koban hologram film "Meiwa Pax Co., Ltd .: Evaporation film" Attack (ATA
C) "Reiko Co., Ltd .: Evaporated polyester film" Dialaster, Sun Mirror, Poly Raster, Multi-mirror "Wase Industries Co., Ltd .: Evaporated polypropylene" Wasei High Fan Evaporated Film "Transparent Evaporated Film Oike Kogyo Co., Ltd .: Transparent high barrier film "MOS" Toyo Metallizing Co., Ltd .: Transparent evaporated film "BARR"
IALOX (VM-PET1011) "Mitsubishi Chemical Kojin Pax Co., Ltd .: Silica-deposited film" Tech Barrier "Reiko Co., Ltd .: Transparent barrier material" Fine Barrier "

A typical embodiment of a molded article for a photographic light-sensitive material of the present invention will be described with reference to the drawings, but the present invention is not limited thereto.

FIGS. 1 to 8 are partial sectional views of a light-shielding film for a photographic light-sensitive material.

The light-shielding film for a photographic light-sensitive material shown in FIG. 1 is formed of a single-layer film comprising only a light-shielding thermoplastic resin film layer 1a as a molded article for a photographic light-sensitive material of the present invention.

The light-shielding film for a photographic light-sensitive material shown in FIG. 2 comprises a light-shielding thermoplastic resin film layer 1a as a molded article for a photographic light-sensitive material of the present invention and a thermoplastic resin film layer 2a to which a light-shielding substance is added. And a two-layer co-extruded film IIa.

The light-shielding film for a photographic light-sensitive material shown in FIG. 3 comprises a light-shielding thermoplastic resin film layer 1a as a molded article for a photographic light-sensitive material of the present invention and a thermoplastic resin film layer 2 containing no light-shielding substance. And a two-layer co-extruded film IIa.

The light-shielding film for a photographic light-sensitive material shown in FIG. 4 comprises a light-shielding thermoplastic resin film layer 1a as a molded article for a photographic light-sensitive material of the present invention and a thermoplastic resin film layer 2a to which a light-shielding substance is added. Are formed by bonding and laminating two light-shielding thermoplastic resin film layers 1a to each other by blocking B.

The light-shielding film for a photographic light-sensitive material shown in FIG. 5 comprises a light-shielding thermoplastic resin film layer 1a as a molded article for a photographic light-sensitive material of the present invention and a thermoplastic resin film layer 2 containing no light-shielding substance. Are formed by bonding and laminating two light-shielding thermoplastic resin film layers 1a to each other by blocking B.

In the light-shielding film for photographic light-sensitive material shown in FIG. 6, a flexible sheet layer 4 is laminated via an adhesive layer 3 on a light-shielding thermoplastic resin film layer 1a as a molded product for photographic light-sensitive material of the present invention. It is formed.

The light-shielding film for a photographic light-sensitive material shown in FIG. 7 comprises a light-shielding thermoplastic resin film layer 1a as a molded article for a photographic light-sensitive material of the present invention and a thermoplastic resin film layer 2a to which a light-shielding substance is added. A two-layer coextruded film IIa made of a flexible sheet layer 4 via an adhesive layer 3
Are laminated.

The light-shielding film for a photographic light-sensitive material shown in FIG. 8 comprises a light-shielding thermoplastic resin film layer 1a as a molded article for a photographic light-sensitive material of the present invention and a thermoplastic resin film layer 2a to which a light-shielding substance is added. A metal thin film-processed flexible sheet (most preferably an aluminum-evaporated biaxially stretched thermoplastic resin film) 6 obtained by processing a metal thin film 5 on a flexible sheet layer 4 via an adhesive layer 3 on a two-layer co-extruded film IIa comprising It is formed by lamination.

Next, a method of manufacturing the light-shielding film for a photographic light-sensitive material shown in FIG. 4 will be described with reference to FIGS.

First, the light-shielding thermoplastic resin film layer 1a
The resin for extruding is applied to the extruder 11, and the resin for the thermoplastic resin film layer 2a to which the light-shielding substance is added is supplied to the extruder 12, and each is heated and melted. Next, the ring die 13
Light-shielding thermoplastic resin film layer 1 from the slit inside
The resin for a is extruded from the outer slit, and the resin for the thermoplastic resin film layer 2a to which the light-shielding substance is added is extruded from the outer slit to form the light-shielding thermoplastic resin film layer 1a and the thermoplastic resin film layer 2a. At this time, as shown in FIG. 10 which is an enlarged sectional view of a part a in FIG. 9, the light-shielding thermoplastic resin film layer 1a and the light-shielding substance are cooled by the compressed air from the blower pipe 14 and the cooling air from the air ring 15. Is added to the thermoplastic resin film layer 2a to form a light-shielding two-layer co-extruded blown film IIa.

The light-shielding two-layer co-extruded blown film IIa is pulled by a take-off squeeze roll (nip roll) 16 and rises through a guide roller 17 and a guide plate 18. Then, the light-shielding thermoplastic resin film layers 1a are adhered to each other by blocking B as shown in FIG. 11, which is an enlarged sectional view of a portion b in FIG. Thus, a light-shielding film for a photographic photosensitive material is completed.

FIG. 12 is a cross-sectional view of a photographic film cartridge container 20 as a molded article for a photographic photosensitive material of the present invention. The photographic film cartridge container 20 is composed of a container body 21 and a lid 22. In this case, both the container body 21 and the lid 22 are molded articles for a photographic material of the present invention.

FIG. 13 is a perspective view of a photographic film cartridge container 30 as a molded article for a photographic light-sensitive material of the present invention. The photographic film cartridge container 30 has a container body 31 and a lid 32 integrally formed. These are formed with the resin composition of the present invention.

FIG. 14 is a front view of a photographic film spool 40 as a molded product for a photographic light-sensitive material of the present invention. The entire photographic film spool 40 is formed of the light-shielding thermoplastic resin composition of the present invention. I have.

FIG. 15 is a cross-sectional view of a photographic film light-shielding case 50 as a molded product for a photographic light-sensitive material of the present invention.
Are integrally formed and are formed of the resin composition of the present invention.

FIG. 16 is an exploded perspective view of a photographic film cartridge 60 as a molded product for a photographic light-sensitive material of the present invention. The photographic film cartridge 60 has a lower case 61 and an upper case 62, and is loaded into these. Spool 6 that winds photographic film and light-shielding paper 64 in a co-wound state
The lower case 61 and the upper case 62 are formed of the light-shielding thermoplastic resin composition of the present invention.

A photographic film cartridge using the molded photographic material of the present invention will be described with reference to FIGS. 17 and 18. 17 and 18, the patrone main body 70 includes an upper case 71 and a lower case 72, each of which is formed of plastic. A spool 73 is rotatably housed inside the cartridge body 70,
A photographic film 74 is wound around the spool 73 in a roll shape.

Each of the upper and lower cases 71 and 72 has a substantially semi-cylindrical shape, and a port portion 75 is formed to project from a part thereof. Upper case 71 and lower case 72
The light-shielding lid 76 is rotatably fitted into the port 75 when the two are fitted. A flat film passage 77 is formed in the light-shielding lid 76, and when the light-shielding lid 76 is turned to the open position, it becomes a passage for the photographic film 74 sent out from the inside of the cartridge body 70. When the light-shielding lid 76 is rotated to the closed position, the opening (the entrance and exit of the photographic film) formed at the end of the port 75 is completely closed, and the inside of the cartridge body 70 is in a light-shielding state.

A projection 78 is formed at the back of the port portion 75 of the lower case 72. This projection 78 is
3 is a guide for picking up the leading end of the photographic film 74 wound around 3 and guiding it to the film passage 77.

The disks 79 and 80 have openings 7 respectively.
9a and 80a are formed. The spool 73 is fitted into a predetermined position of the spool 73 by being inserted into the openings 79a and 80a, and is rotatably mounted on the spool 73. Lips protrude from the outer circumferences of the disks 79 and 80 so as to face each other, and partially wrap the outermost circumference of the photographic film 74 wound on the spool 73 from both end faces.

When the display component 83 is fitted into the spool 73, the clutch claw 84 and the locking hole 85 of the disk 80 lock with each other when the spool 73 rotates in the film feeding direction. Disk 80
Can be forcibly rotated. When the spool 73 is rotated in the film winding direction, the disk 80 can rotate freely without engaging the clutch claws 84 with the engagement holes 85 of the disk 80. Also, the other disk 7
9 remains rotatable with respect to the spool 73. In addition,
The used display component 83 is integrated with a fan-shaped display plate 83a, and the use state of the photographic film cartridge can be determined by checking its position through a display window formed in the cartridge body 70.

[0239] Side ribs 86 are provided on the inner walls of the side surfaces of the upper case 71 and the lower case 72 to restrict the disks 79 and 80 from spreading out. A sector plate 87 is fixed to the spool 73, and a data flange label 88 is affixed to the surface thereof. A bar code is radially written on the label 88, and the bar code is photoelectrically detected through a window formed on a side surface of the cartridge body 70 when the spool 73 is rotated. This makes it possible to electrically detect the type information, the number of shots, and the like of the photographic film 74 stored in the cartridge body 70. In addition,
On a label 90 attached to the patrone main body 70, a film type indication, a unique number of the patrone, and the like are displayed.

The spool lock component 91 locks the spool 73 so that it does not rotate when the light shielding cover 76 is turned to the closed position. This lock is released when the light shielding cover 76 moves to the open position. Reference numeral 92 denotes a lock pole integrally formed with the upper case 71, and the light blocking cover 76 is locked by the lock pole 92 when it is turned to the closed position. This lock is disclosed by an opening mechanism of a light shielding cover 76 provided in a device such as a camera or a display device when the photographic film cartridge is set in the device. Instead of using the light-shielding lid 76, a film passage may be formed in the inner wall of the port portion 75, and the inside of the patrone body 70 may be kept light-tight by attaching a telemump to the film passage.

[0241] As shown in FIG.
Is completely wound in the cartridge body 70, the outermost periphery of the photographic film 74 is the disk 79, 80.
Are partially wrapped by the lips 81, 81, thereby preventing the winding from being loosened from the spool 73. Thus, when the spool 73 rotates in the feeding direction of the photographic film 74, the photographic film 74 rotates integrally with the spool 73.

The side ribs 86 provided on the inner side walls of the upper and lower cases 71 and 72 regulate the discs 79 and 80 so that they do not spread out from each other. , Facing side ribs 86
The spacing between them has been increased. For this reason, when the leading edge of the photographic film 74 is scooped up by the projection 78 and the disk 79, 80 is slightly spread outward when going to the film path 77, the photographic film 74 is lip 81, 8
A gutter-shaped curl is made and sent out from between the two.

The same effect can be expected even if the side ribs 86 are provided on only one side. Further, as a method of releasing the film winding looseness of the lip 81, a pair of separation claws are provided on both sides in the film width direction, and the pair of lips are partially separated from each other on the outer surfaces of the pair of separation claws in a direction away from each other. You may make it always deform.

When the photographic film cartridge is loaded into the camera, the locking of the light blocking cover 76 by the lock pole 92 is released by the mechanism on the camera side, and then the light blocking cover 76 is rotated in the opening direction. Thereafter, the spool 73 is driven in the feeding direction, and feeding of the photographic film 14 is started. Lip 8 formed on the outer circumference of disks 79 and 80
Since the reference numerals 1 and 81 prevent the photographic film 74 from loosening, the photographic film 74 rotates integrally with the spool 73. During this rotation, the leading end of the photographic film 74 is picked up by the protrusion 78 and guided to the film passage 77.

When the leading end of the photographic film 74 is guided to the film passage 77 in this manner, the lips 81, 81 are pushed out on both sides by the photographic film 74, so that the wrapping of the photographic film 74 is released behind the film passage 77. The one disc 80 is forcibly rotated in the feeding direction by the engagement between the clutch claws 84 and the locking holes 85, so that the force for feeding the photographic film 74 is increased.
Thus, the photographic film 74 is fed out of the cartridge body 70.

At the time of rewinding, the spool 73 is rotated in the reverse direction. Since the rear end of the photographic film 74 is locked to the spool 73, the photographic film 74 is wound into the cartridge body 70 by the reverse rotation of the spool 73. At this time, the discs 79 and 80 are spread behind the film passage 77, and the photographic film 74 is drawn between the discs 79 and 80 and wound around the spool 73.

As shown in FIG.
Have the same contour shape. Openings 79a, 8
0 a is formed on a surface 99 that is one step lower than the surface 98 on which both ends of the photographic film 74 are aligned. The lip 81 protrudes from the outer periphery of the surface 98 so as to face the other disks 79 and 80, respectively, and partially wraps the outermost periphery of the photographic film 74 wound on the spool 73 from both end surfaces.

A flange 82 is integrally provided on the outer periphery of the lip 81. The flange 82 functions to reinforce the lip 81 so as not to spread. Also, in order to have a function of guiding the photographic film 74 to easily enter the inside of the lip 81 at the time of film winding,
The flange 82 has a cross-sectional shape that is inclined such that the tips of the opposing surfaces 82a are separated from each other.

FIG. 21 is an exploded perspective view of a film unit with a lens 100 as a molded product for a photographic photosensitive material of the present invention. The film unit with a lens 100 accommodates a spool 101 around which a photographic film is wound in a light-tight manner. A lower case 103 for further storing the photographic film cartridge 102 in a light-tight manner, and an upper case 104 for sealing the lower case 103 from light. The lower case 103 and the upper case 104 according to the present invention. Although formed of a resin composition, the conventional one is formed of a light-shielding thermoplastic resin composition such as a polystyrene resin containing carbon black, a polymethyl methacrylate resin, and a polycarbonate resin. On the other hand, the lens 105 and the finder 106 are made of a non-colored polycarbonate resin (displayed as PC) and a polystyrene resin (displayed as PS resin).
And a transparent thermoplastic resin composition such as polymethyl methacrylate resin (denoted as PMMA resin).

FIG. 22 is a plan view of a container for a photographic film cartridge as a molded article for a photographic light-sensitive material of the present invention.
FIG. 24 is a partially cutaway sectional view of the photographic film patrone container, FIG. 24 is a perspective view of the photographic film patrone container with the cover removed, and FIG. 25 is the photographic film patrone container with the cover removed. FIG.

This container for photographic film patrone is composed of a container body 111 and a lid 112.
A groove 113 is formed in the lid 112, and a groove 1 is formed in the lid 112.
13 are formed with protrusions 114 to be fitted. The lid 112 is formed with a protruding portion 115 protruding outward from the container body 111.

FIG. 26 is a perspective view of the belt-shaped photosensitive material core 120 as a molded product for a photographic photosensitive material of the present invention, which is located on the side opposite to the resin injection port. It is formed of things. The inner surface of the outer cylinder 121 of the band-shaped photosensitive material core has a height of 0.0001 to
A plurality of 0.07 mm annular ridges 122 are provided to improve the injection moldability, physical strength, and appearance of the belt-shaped photosensitive material core.

FIG. 27 is a perspective view of a bag-containing sheet film holder as a molded product for a photographic material of the present invention.
The sheet film holder 130 is mounted on the back of the camera, and is used for taking in and out a photographic film in a bag.

FIG. 28 is a perspective view of a packaged sheet photographic film holder as a molded product for a photographic light-sensitive material of the present invention. 1
41 is put in and out.

FIG. 29 is a perspective view of a film unit package with a lens. In the film unit package with a lens 150, a film unit with a lens is sealed and stored in a packaging bag 151 as a molded product for a photographic photosensitive material of the present invention. It is manufactured by doing.

FIG. 30 is a perspective view of a 35 mm photographic film assembly package with a patrone.
The photographic film assembly package 160 is provided with a transparent plastic case 162 as a molded product for a photographic light-sensitive material of the present invention in which a substrate 161 is kneaded with a desiccant, and a 35 mm photographic film (abbreviated as APS) containing a resin patrone therein.
Film 163 is stored.

FIG. 31 is a sectional view of the photographic film cartridge main body 170 constituting the photographic photosensitive material package of the present invention. The patrone main body 170 includes a metal base (preferably tin-free steel having a thickness of 0.15 to 0.35 mm) 171, a white pigment-containing undercoat layer 172 applied to the outer surface of the metal base 171, and the undercoat layer 172. Layer 174 comprising a colored ink layer 173 such as a brand name, a pattern, a CI mark, a bar code, etc. printed on the surface of
And a transparent or translucent protective layer 175 provided on the outer surface of the colored layer 174. Metal substrate 17
A black coating layer 176 containing carbon black is formed on the inner surface of the substrate 1. If necessary, a protective layer may be provided on the surface of the black coating layer 176. The cap for sealing both ends of the patrone main body 170 and the spool housed therein are made of the molded product for a photographic material of the present invention. While the photographic film is wound around the spool, it is sealed and packaged in the photographic film container shown in FIGS.

[0258]

EXAMPLES [Products of the present invention 1-5, comparative products 1-5] Melt flow rate (JIS K 6758, temperature 230 ° C, piston load 2.16 kg) is 12 g / 10 min, density (JI
SK 6758) is 0.90 g / cm ³ , and the flexural modulus (JI
SK 6758) is 11,000 kg / cm ² , and Izod impact strength (JIS K 6758) is 2.5 kg · cm.
/ Cm, Rockwell hardness (R scale of JIS K 6758) is 95R, Vicat softening point (JIS K 675)
8) is 95 ° C, the low-temperature embrittlement temperature (JIS K 6758) is 12 ° C, and the heat distortion temperature (JISK 7207) is 118 ° C.
A lubricant, a surfactant, an antioxidant, a plasticizer, and an organic nucleating agent were added to 100 parts by weight of the propylene / ethylene random copolymer resin (ethylene content: 3 mol%) in the amounts shown in Table 2. As the lubricant, oleic acid amide was used. As the antioxidant, Irganox 1010 (tetrakis [ethylene-3- (3 ′, 5′-dibutyl-4), a hindered phenolic antioxidant manufactured by Ciba Geigy) was used. -Hydroxyphenyl) propionate]}, an alicyclic saturated hydrocarbon compound having three or more cyclohexyl rings as a plasticizer, and a gel ol MD {manufactured by Shin Nippon Rika KK as an organic nucleating agent. Screw (p-
(Methylbenzylidene) sorbitol｝ was used. In addition, 0.1 part by weight of calcium stearate was added to all the products as a halogen compound neutralizer.

Then, the melt flow rate and the low-temperature embrittlement temperature of the above resin composition were measured. Table 2 shows the results.

Using the above-mentioned polypropylene resin composition, roll kneading was performed at 190 ° C. for 5 minutes.
A 1 mm sheet was prepared by pressing for 1 minute.
Then, the transparency and bleed-out property of this sheet were visually evaluated. Table 2 shows the results.

Further, using the above-mentioned polypropylene resin composition, a photographic film cartridge container corresponding to FIG. 24 was prepared at a resin temperature and a molding cycle shown in Table 2. Nestal (trade name, mold clamping pressure: 150 t) manufactured by Sumitomo Heavy Industries, Ltd. was used as an injection molding machine, and a hot runner type 24-cavity (number of cavities) was used as a mold.

Then, the photographic film patrone container was tested for photographic properties and crack generation rate from a height of 5 m.
Table 2 shows the results.

[0263]

[Table 2]

The evaluations in Table 2 are shown below. ◎… Excellent ○ …… Excellent ● …… Practical limit ▲… Improvement required × …… Practical use difficult

The test methods in Table 2 are shown below.

<Transparency> Line thickness 0.5 mm, interval 2 m
The sheet was placed between the eye and the transparency inspection drawing sheet in which m parallel lines were drawn on a blank sheet, and the sheet was moved away from the eyes. The evaluation was made by the distance at which the parallel lines of the transparency inspection drawing sheet behind the sheet became invisible.

<Bleed-out Property> The stickiness and white powder generation on the surface were visually observed and evaluated.

<Photographic Properties> A negative color photographic film having an ISO sensitivity of 400 was stored and stored under the conditions of 35 ° C. and 70% RH.
Left for months. Thereafter, the film was developed, and the increase in fog, the change in sensitivity, the change in color development, and the change in gradation were evaluated by comparison with the values before leaving (blank).

<Crack generation rate from 5 m height at 0 ° C. condition> 0
Visually evaluate the occurrence of cracks or cracks in the photographic film patrone container body when dropped on a concrete floor from a height of 5 m in a state in which 36 photographic films are sealed and packaged at a temperature of ℃. did.

[Product A of the Present Invention]
Instead of the ethylene random copolymer resin, MFR (A
STM D-1238 E condition, measured at 190 ° C., piston load 2.16 kg) was 15 g / 10 min, density (AS
TMD-1505) is 0.960 g / cm ³ , molecular weight distribution (weight average molecular weight / number average molecular weight measured by gel permeation chromatography) is 2.6, and flexural modulus (ASTM D-790) is 12,800 kg / C
m ^2, (notched ASTM D-256) Izod impact strength ethylene 8 kg · cm / cm 99.9 mol%
Except for using a polyethylene-based resin containing butene-1 in an amount of 0.1 mol%, a container for a photographic film cartridge made of the same resin composition in both types and amounts of additives.

This product A of the present invention is similar to product 2 of the present invention,
It was excellent in moldability, physical strength, photographic properties, bleed-out resistance, transparency, appearance and the like. In addition, since there is little occurrence of molding failure and the molding cycle can be greatly shortened, the container for photographic film cartridges is inexpensive and has excellent quality and appearance.

[Product B of the Present Invention] The MFR (condition E of ASTM D-1238) produced by polymerization using a metallocene catalyst was 4 g / 10 min, and the density (ASTM D-1505) was 0.1 g / ml.
90 parts by weight of an ethylene-hexene-1 copolymer resin having a melting point of 905 g / cm ³ , a melting point of the DSC method of 98 ° C., a Vicat softening point (ASTM D-1525) of 78 ° C. and a molecular weight distribution of 2.5, and a radical weight of the high pressure method 2. MFR manufactured by law.
2 g / 10 min, density 0.922 g / cm ³ , DSC melting point 110 ° C., Vicat softening point 83 ° C., molecular weight distribution 5.4.
3 parts by weight of furnace carbon black produced from ethylene bottom oil using naphtha as a raw material, 0.1 part by weight of calcium stearate as a lubricant, 0.05 part by weight of erucamide with respect to 100 parts by weight of an L-LDPE resin.
0.1 parts by weight of a fatty acid ester of stearic acid monoglyceride as an antistatic agent, and a hindered phenolic antioxidant (Irg, manufactured by Ciba-Geigy KK) as an antioxidant
0.05 parts by weight of anox 1076), 0.05 parts by weight of a phosphorus-based antioxidant (Irgafos 168, manufactured by Ciba-Geigy KK), and a silver-based antibacterial agent ( Gel Technology K
K, Bactenone AZ) containing 5 parts by weight of a zinc compound having an average secondary particle diameter of 0.8 μm and 10 parts by weight of a liquid alicyclic saturated hydrocarbon compound having three cyclohexyl rings as a plasticizer. Using a resin composition, an air-cooled blown film molding machine (resin temperature 180 ° C., ring die diameter 100 mm, lip gap 1.0 mm, blow ratio 1.7, L / D22), drawdown ratio 40, thickness 50
A μm light-shielding blown film was formed.

This light-shielding blown film is
Good photographic and light-shielding properties, reduced bleed-out of additives, reduced low-temperature embrittlement temperature, improved fluidity of resin composition, improved compatibility of additives, recycled resins, and blended resins However, the occurrence of bumps (foreign masses) and microgels was reduced, the dispersibility of pigments and dyes was improved, the film formability was excellent, and the odor was reduced.

[0274]

The present invention is configured as described above.
The following effects can be obtained without deteriorating various characteristics essential for molded articles for photographic photosensitive materials. i) Transparency is improved (when no light-shielding substance is added). ii) Bleed-out of additives (additives that easily bleed out, such as lubricants, surfactants, and antioxidants) is reduced. iii) The low-temperature embrittlement temperature decreases (the drop strength at low temperatures improves). iv) The fluidity of the resin composition is improved, and the MFR is increased.
As a result, in the case of injection molding, the molding cycle can be shortened, and in the case of film molding, the film molding speed can be improved (the effect of reducing the occurrence of melt fracture). v) The compatibility of additives, recycled resins, and blended resins is improved, and the occurrence of weld lines, bumps, microgels, and the like is reduced, and the physical strength and appearance are improved. vi) The dispersibility of pigments and dyes is improved. vii) Odor is reduced. viii) Photographic properties are improved.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view of a light-shielding film for a photographic light-sensitive material, which is an embodiment of a molded article for a photographic light-sensitive material of the present invention.

FIG. 2 is a partial cross-sectional view of a light-shielding film for a photographic light-sensitive material, which is an embodiment of a molded article for a photographic light-sensitive material of the present invention.

FIG. 3 is a partial cross-sectional view of a light-shielding film for a photographic light-sensitive material, which is an embodiment of the molded article for a photographic light-sensitive material of the present invention.

FIG. 4 is a partial cross-sectional view of a light-shielding film for a photographic light-sensitive material which is an embodiment of the molded article for a photographic light-sensitive material of the present invention.

FIG. 5 is a partial cross-sectional view of a light-shielding film for a photographic light-sensitive material which is an embodiment of the molded article for a photographic light-sensitive material of the present invention.

FIG. 6 is a partial cross-sectional view of a light-shielding film for a photographic light-sensitive material which is an embodiment of the molded article for a photographic light-sensitive material of the present invention.

FIG. 7 is a partial cross-sectional view of a light-shielding film for a photographic light-sensitive material which is an embodiment of the molded article for a photographic light-sensitive material of the present invention.

FIG. 8 is a partial cross-sectional view of a light-shielding film for a photographic light-sensitive material which is an embodiment of the molded article for a photographic light-sensitive material of the present invention.

FIG. 9 is a schematic view of an apparatus for manufacturing a light-shielding film for a photographic light-sensitive material, which is an embodiment of the molded article for a photographic light-sensitive material of the present invention.

FIG. 10 is an enlarged sectional view of a part a in FIG. 9;

FIG. 11 is an enlarged sectional view of a portion b in FIG. 9;

FIG. 12 is a cross-sectional view of a photographic film container which is an embodiment of the molded product for a photographic light-sensitive material of the present invention.

FIG. 13 is a cross-sectional view of a photographic film container integral with a lid, which is an embodiment of the molded product for a photographic light-sensitive material of the present invention.

FIG. 14 is a cross-sectional view of a spool for a photographic film which is an embodiment of the molded article for a photographic photosensitive material of the present invention.

FIG. 15 is a cross-sectional view of a light-shielding case for a photographic film having a rectangular shape with a lid, which is an embodiment of the molded product for a photographic photosensitive material of the present invention.

FIG. 16 is an exploded perspective view of a photographic film cartridge which is an embodiment of the molded product for a photographic photosensitive material of the present invention.

FIG. 17 is an exploded perspective view of a resin-made photographic film cartridge which is an embodiment of the molded product for a photographic light-sensitive material of the present invention.

FIG. 18 is a side view of a resin photographic film cartridge which is an embodiment of the molded product for photographic photosensitive materials of the present invention.

FIG. 19 is a cross-sectional view of a resin-made photographic film cartridge which is an embodiment of the molded article for photographic light-sensitive materials of the present invention.

FIG. 20 is a partial cross-sectional view of a disk used for a resin-made photographic film cartridge which is an embodiment of the molded product for a photographic light-sensitive material of the present invention.

FIG. 21 is an exploded perspective view of a film unit with a lens, which is an embodiment of a molded product for a photographic light-sensitive material of the present invention.

FIG. 22 is a plan view of a container for a photographic film cartridge which is an embodiment of the molded product for a photographic photosensitive material of the present invention.

FIG. 23 is a partially cutaway cross-sectional view of a container for a photographic film cartridge which is an embodiment of the molded product for a photographic light-sensitive material of the present invention.

FIG. 24 is a perspective view of a molded article for a photographic light-sensitive material of the present invention in a state where a lid of a container for a photographic film cartridge is removed.

FIG. 25 is a plan view showing a state in which a cover of a container for a photographic film cartridge which is an embodiment of the molded product for a photographic photosensitive material of the present invention is removed.

FIG. 26 is a perspective view of a belt-shaped photosensitive material core which is an embodiment of the molded product for a photographic photosensitive material of the present invention.

FIG. 27 is a perspective view of a bag-containing sheet film holder that is an embodiment of the molded product for a photographic photosensitive material of the present invention.

FIG. 28 is a perspective view of a packaged sheet photographic film holder which is an embodiment of the molded product for a photographic photosensitive material of the present invention.

FIG. 29 is a perspective view of a packaging bag that is an embodiment of the photographic photosensitive material package of the present invention.

FIG. 30 is a perspective view of a transparent plastic case which is an embodiment of the photographic photosensitive material package of the present invention.

FIG. 31 is a sectional view of a photographic film cartridge main body which is an embodiment of the photographic photosensitive material package of the present invention.

[Explanation of symbols]

1a: Light-shielding film layer for photographic light-sensitive material (molded article for photographic light-sensitive material) 2, 2a: Thermoplastic resin film layer 3: Adhesive layer 4: Flexible sheet layer a: Indicates that a light-shielding substance is included. B: Indicates blocking.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 3/00 560 G03C 3/00 560P 585 585C

Claims (4)

[Claims] 1. A thermoplastic resin (however, a vinyl chloride resin,
(Excluding vinylidene chloride resin and chlorinated polyolefin resin), the total content of at least one of a lubricant, a surfactant, and an antioxidant is 0.001 to 100 parts by weight.
20 parts by weight and the content of one or more plasticizers 0.1 to 15
A molded article for a photographic light-sensitive material, which is molded using a resin composition obtained by mixing 0 parts by weight. 2. A molded article for a photographic light-sensitive material according to claim 1, wherein 50% by weight or more of said thermoplastic resin is a polyolefin resin. 3. The molded article for a photographic material according to claim 1, wherein the plasticizer is an alicyclic saturated hydrocarbon compound having three or more cyclohexyl rings. 4. A photographic light-sensitive material, the molded article for a photographic light-sensitive material according to claim 1, wherein the photographic light-sensitive material is applied, and a sealed package of the molded article for a photographic light-sensitive material.
Moisture permeability according to the condition B measurement method of IS Z 0208 is 1
A moisture-proof packaging material of 0 g / m ² · 24 hours or less.