JP3070684B2 - Packaging materials for photosensitive materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a packaging material for photographic light-sensitive materials.

[Conventional technology]

Various types of packaging materials for photographic light-sensitive materials have been widely put into practical use, and various performances are required according to their uses.

As a packaging material for photographic light-sensitive materials that loses its quality value when exposed to light, it completely blocks light, and the required properties include photographic properties, suitability for packaging material slits, gas barrier properties, light shielding properties, moisture resistance, rigidity, Physical strength (rupture strength, tear strength, impact puncture strength, gelbo test strength, abrasion strength, etc.), heat sealability (heat seal strength, hot tack property, impurities sealing property, etc.), antistatic property, flatness, slip properties, etc. Is mentioned.

However, it is very difficult to combine these properties with a single film material, and a packaging material having a plurality of layers has been used in the past. For example, Japanese Patent Publication 63-37700
The invention disclosed in the above publication is a packaging bag made of a packaging material in which a polyester film layer is disposed outside an aluminum layer, and a polyolefin resin layer containing a light-shielding material and a nonionic antistatic agent is disposed inside the aluminum layer.

Further, the present inventor has also proposed a water-absorbing, dust-free, heat-resistant flexible sheet layer on both sides of a metal layer via an adhesive layer, a carbon black, an antioxidant and a linear low-density polyethylene (hereinafter referred to as L-LDPE). A gusset bag using a packaging material in which a polyolefin-based resin film layer containing a resin is laminated has been proposed (JP-A-63-272668).

[Problems to be solved by the invention]

However, in conventional packaging materials, the photosensitive material having a shock or sharp edges may cause breakage or pinholes, and in particular, portions where pressure is applied more than other portions, such as a gusset portion of a bottom heat seal portion in a gusset bag. In this case, the heat seal was apt to break, so that folding was required, and the antistatic property of peeling off the outer layer was not perfect.

An object of the present invention is to provide an inexpensive packaging material which has the above-mentioned problems and has physical strength that can be dealt with without folding the bottom seal of a gusset bag, is excellent in light shielding properties, and is inexpensive.

[Means for solving the problem]

The present invention solves the above-mentioned object by using a packaging material in which an aluminum-evaporated biaxially stretched thermoplastic resin film, a light-shielding polyolefin-based resin film, and kraft paper are laminated.

That is, the present invention is an aluminum-deposited biaxially stretched thermoplastic resin film, the melt index is laminated on one surface of the thermoplastic resin film is 0.8 to 10 g / 10 minutes,
A light-shielding polyolefin-based resin film containing an ethylene / α-olefin copolymer resin having a density of 0.870 to 0.940 g / cm ³ as a main component and further containing carbon black, an antiblocking substance, 0.003 to 2.0% by weight of an antioxidant and a lubricant; And a kraft paper laminated on the other surface of the thermoplastic film via a light-shielding polyolefin-based resin adhesive layer, and a photographic paper packaging material used for a single gusset bag. is there.

As the aluminum-deposited biaxially stretched thermoplastic resin film used in the present invention, various commercially available aluminum-deposited biaxially stretched thermoplastic resin films can be used, and an aluminum-deposited film is deposited on a biaxially stretched thermoplastic resin film having excellent physical strength. It is processed.

This aluminum-deposited biaxially stretched thermoplastic resin film has light-shielding properties, moisture-proof properties, gas barrier properties, impact drilling strength,
It has an excellent bursting strength, a higher Young's modulus than the light-shielding polyolefin resin adhesive layer, and has an excellent resistance to an impact from the outside and inside of the packaging material as a middle layer and to damage by sharp objects.

The biaxially stretched thermoplastic resin film may be formed in a vertical direction (MD direction) and a horizontal direction (CD direction) by a known biaxial stretching method such as simultaneous biaxial stretching or sequential biaxial stretching.
It is a film having a higher Young's modulus than the light-shielding polyolefin resin adhesive layer stretched 1.5 to 20 times, preferably 3 to 15 times. As the thermoplastic resin used for this film,
Polyester resin, polyamide (nylon) resin, polyethylene resin, polystyrene resin, polypropylene resin, polyolefin copolymer resin, polyvinyl chloride resin, polyvinylidene chloride resin, eval resin, vinylon resin, co-polymerization of these resins and other resins Coalescing resin (including not only a binary copolymer resin but also a tertiary or higher copolymer resin. The copolymer mode may be random copolymerization or block copolymerization), the above resin and other resins And the like.

Examples of the polyester resin include resins synthesized from dimethyl terephthalate and ethylene glycol, dimethyl terephthalate and 1,4-cyclohexanehexane, dimethyl terephthalate and dimethyl isophthalate. Nylon 6, nylon for polyamide resin
66, nylon 12, nylon 11, and nylon 6-66 copolymer resin.

Then, these resins are biaxially stretched by a T-die film forming machine or an inflation film forming machine to form a film.

This biaxially stretched thermoplastic resin film has a thickness of 5 to reduce the thickness of the packaging material, reduce costs, and secure physical strength.
It is preferably about 70 μm. When the thickness is less than 5 μm, wrinkles and cuts are apt to occur in the laminating process. When the thickness exceeds 70 μm, the rigidity is too large, the bag making property, the gelbo test strength and the handling property are deteriorated, and the cost becomes high. Not preferred.

Further, the biaxially stretched thermoplastic resin film may be a single layer or a multilayer coextruded film of two or more layers.
The difference in elongation at break between longitudinal and transverse breaks is within 2 times, preferably 1.5 times.
It is desirable that it is within twice to facilitate hand tear without difference in length and width.

The thickness of the deposited aluminum film is preferably 55 to 1200 mm in terms of physical strength, light-shielding property, antistatic property, moisture-proof property, gas barrier property, cost and quality as a laminate. That is, if the thickness is less than 55 °, the charge generated in the layers on both sides of the aluminum vapor deposition film cannot be reduced. Also, if the thickness is 12
When it exceeds 00 °, antistatic, gas barrier, moisture-proof and light-shielding properties can be ensured, but cost and vacuum evaporation methods may cause deterioration of the biaxially stretched thermoplastic resin film due to heating and decrease in physical strength of the resulting laminated film. There is a problem in point. In particular, 80
~ 800mm thickness is preferred, more preferably 100 ~ 600
Å.

In order to deposit an aluminum deposition film, a vacuum deposition method, a sputtering method, an ion plating method, an electron beam deposition method, or the like is used.

The aluminum vapor-deposited film may be vapor-deposited not only on one side but also on both sides of the biaxially stretched thermoplastic resin film. Applying an anchor coat agent on the surface of the biaxially stretched thermoplastic resin film on which the aluminum vapor deposition film is deposited, corona discharge treatment,
It is preferable to perform a frame treatment or the like because the adhesion strength of the aluminum vapor-deposited film can be increased.

A protective layer can be provided on the aluminum deposition film in order to prevent scratching and peeling. As this protective layer, butyral resin, acrylic resin, cellulose resin such as acetate cellulose, urethane resin, epoxy resin, polyester resin, ionomer resin, ethylene-ethyl acrylate copolymer resin, various polyethylene resins, polypropylene resin, etc. Resin can be used.

Also, wax, gelatin, polyvinyl alcohol, and the like can be used.

The protective layer is preferably formed to have an extremely thin thickness. Even when the protective layer is provided by an extrusion lamination method, static electricity is not sufficiently removed unless the thickness is 50 μm or less.

When the thickness is 5 μm or less by a known solution coating method, a spray coating method, or the like, the aluminum deposited film can be protected and the effect of removing static electricity is large.

A light-shielding polyolefin-based resin film is laminated on one surface of the aluminum-deposited biaxially stretched thermoplastic resin film. This light-shielding polyolefin resin film contains an ethylene / α-olefin copolymer resin, carbon black, an anti-blocking substance, an antioxidant and a lubricant, and prevents light penetration due to a piping effect from the cross section and poor light shielding due to pinhole generation. It is intended to prevent and improve heat sealability (heat seal strength, heat seal strength retention with time, hot tack property, foreign matter sealability), physical strength, and the like.

The L-LDPE (Liner Low Density Polyetylene) resin, which is the ethylene / α-olefin copolymer resin of the present invention, is referred to as a third polyethylene resin. It is a low-cost, high-strength resin that meets the needs of the age of resources. This resin is a copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 13 carbon atoms, preferably 4 to 10 carbon atoms by a low-pressure method or a high-pressure improvement method, and has a linear linear short-branched structure. 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,
Heptene-1 or the like is used.

Although the density is generally considered to be about the same as that of a low-medium density polyethylene resin, many commercial products have a density in the range of 0.87 to 0.95 g / cm ³ . The melt index is often in the range of 0.1 to 50 g / 10 minutes.

As the polymerization process of the L-LDPE resin, there are a gas phase method using a medium / low pressure apparatus, a liquid phase 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 (Nippon Unicar) Ethylene / 4-methylpentene-1 copolymer resin Ultoxex (Mitsui Petrochemical) Ethylene / octene-1 copolymer resin Stamilex (DSM) Dourex (Dow Chemical) Screa ( DuPont Canada) MORETEC (Idemitsu Petrochemical) These L-LDPE Those used in the present invention in terms of physical strength and heat seal strength and film formability in the butter, melt index (hereinafter MI and display) is 0.8~10g / 1
0 minutes (JIS K-6760), density 0.870-0.940 g / cm ³ (JIS K
-6760), preferably obtained by a liquid phase process and a gas phase process having 6 to 8 carbon atoms of an α-olefin.

Particularly preferred representative examples are listed by trade names: Ultex and Mitsui Petrochemical Co., Ltd., in which 4-methylpentene-1 having 6 carbon atoms is introduced into polyethylene as an α-olefin side chain, and α-olefin side chain. MORETEC of Idemitsu Petrochemical Co., Ltd.
And DSM's Stamirex and Dow Chemical's Dourex (the L
-LDPE resin. ).

Preferable typical examples obtained by the low-pressure gas phase process are listed below under trade names, such as those of Nippon Unicar Co., Ltd., in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain.
There are TUFLIN and TUFTHENE of UCC.

Also recently launched ultra low density linear low density polyethylene resin having a density of less than 0.910 g / cm ³ , such as NUC-FL of UCC
X and Exelen VL of Sumitomo Chemical Co., Ltd. are also preferable.
Α-Olefin is 4-carbon butene-1 for both company products).

The carbon black is used mainly to secure light-shielding properties, to prevent oxidation of the resin, and to improve physical strength.

This carbon black is classified into gas black, oil furnace black, Ketjen black, anthracene black, acetylene black, oil smoke, pine smoke, furnace black, channel black, graphite, thermal black, lamp black and the like depending on the raw material.

In the packaging material of the present invention, furnace carbon black is preferred for the purpose of improving light-shielding properties, cost and physical properties, and acetylene carbon black and Ketjen carbon black are preferred as light-shielding substances which are expensive but have an antistatic effect. If necessary, it is also preferable to mix the former and the latter according to required characteristics. However, Ketjen carbon black is liable to generate fog, so that selection of raw materials and countermeasures for photographic emulsions are sometimes required. On the other hand, among these carbon blacks, ph 6.0 to 8.5, average particle diameter 15 to 50 mμ, volatile matter 3% or less, oil absorption 60cc / 100g
The above acetylene carbon black or furnace carbon black is particularly preferred. By using such carbon black, the occurrence of fog is small,
It is possible to produce a packaging material having a number of advantages such as little increase / decrease in photosensitivity, high light-shielding ability, excellent dispersibility, and less occurrence of bumps, fish eyes and pinholes.

Use shapes of carbon black include dry color, liquid color, paste color, master batch pellets,
There are compound color pellets, granular color pellets, etc., but master batch pellets are most preferred in terms of suitability for use and cost. For example, as a colored pellet in the master batch method, a light-shielding polyolefin-based material is prepared using a master batch pellet having a carbon concentration of 40%. When a resin film or a light-shielding polyolefin-based resin adhesive is colored, it can be manufactured at a cost of 30% or more less than coloring by a compound method.

Representative domestic carbon black suppliers include Mitsubishi Kasei Kogyo KK, Asahi Carbon KK, Tokai Carbon KK,
Showa Cabot KK, Electrochemical KK, Hokutan Carbon KK, Nippon Steel Chemical KK, Toyo Continental Carbon Co., Ltd.

Representative commercial names of the anti-blocking substances are shown below.

(1) Inorganic (a) silica; Syloid 244 (Fuji Davison), Syloid 978 (Da
vison), Celite High Flow Supercell (Johns-Ma
nville), Celite Super Floss (Johns-Manvill)
e), AEROSIL200 (Nippon Aerosil), AEROSIL300 (Nippon Aerosil), Super Light (Kono Shoten), Snow Light (Mori Shoten), Radio Light W (Showa Chemical) (b) Calcium silicate; Microcell C (Johns-Manville) Microcell T-38 (Johns-Manville) (c) Aluminum silicate; P-820 (Deggossa), Perlite 54 (Toko Perlite), (d) Talc; PKN (Hayashi Kasei), Micro White (Hayashi Kasei) ( e) Calcium carbonate; Softon SS (DOW) (2) Organic higher fatty acid polyvinyl ester, dicarboxylic acid ester amide, n-octadecyl urea, N, N'-dioleyl oxamide Also has an anti-blocking effect and prevents static. Representative examples of surfactants that are preferably incorporated also in the point of (1) above include, as cationic surfactants, primary amines ,
There are tertiary amines, quaternary ammonium compounds, and pyridine derivatives, and as anionic activators, fatty acid metal salts,
There are alkyl sulfates, alkyl naphthalene sulfonates, and succinate sulfonates, and nonionic surfactants include partial fatty acid esters of polyhydric alcohols, ethylene oxide adducts of fatty alcohols,
There are ethylene oxide adducts of fatty acids, ethylene oxide adducts of fatty amino or fatty acid amides, ethylene oxide adducts of alkylphenols, and ethylene oxide adducts of alkyl naphthols.Amphoteric activators include carboxylic acid derivatives, imidazoline derivatives and the like. is there.

On the other side of the aluminum vapor-deposited biaxially stretched thermoplastic resin film, kraft paper having heat resistance and a high Young's modulus is laminated, and this kraft paper has excellent bag making suitability and curling prevention, Provides resistance to external impacts and sharp edges.

When used as the outermost layer of packaging materials for photographic materials, bleached kraft paper has printability, writability, high physical strength, excellent suitability for bag making, does not melt, and does not generate pinholes. This is particularly preferred in view of the above.

The aluminum-deposited biaxially stretched thermoplastic resin film and the kraft paper are adhered by a light-shielding polyolefin-based resin adhesive layer containing a light-shielding substance.

This light-shielding polyolefin resin adhesive layer is mainly composed of a polyolefin resin. For example, various polyethylene resins, various ethylene copolymer resins, various modified polyolefin resins, and the like are used, and in particular, LDPE resin, L-LD
PE resins and mixed resins of these with other polyolefin resins are preferred.

The light-shielding polyolefin-based resin adhesive layer preferably has a thickness in the range of about 10 to about 60 μm from the viewpoint of securing adhesive strength and light-shielding properties. When the thickness is less than about 10 μm, it is difficult to secure light-shielding properties only with the light-shielding polyolefin-based resin adhesive layer alone, pinholes are easily generated, adhesive strength is insufficient, and delamination is apt to occur. On the other hand, if the thickness exceeds about 60 μm, the kraft paper and the aluminum-deposited biaxially stretched thermoplastic resin film are degraded by heat or are thermally shrunk to increase curling, and the adhesive strength is increased and the notch effect is lost. Reduces tear strength. Further, the laminating speed is reduced, the amount of resin used is large, and the cost is high.

Examples of the light-shielding substance contained in the light-shielding polyolefin-based resin adhesive layer are shown below.

(1) Inorganic compounds A. Oxides: silica, diatomaceous earth, alumina, titanium oxide,
Iron oxide, zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite,
B. Hydroxides: aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate C. Carbonates: calcium carbonate, magnesium carbonate, dolomite, dawsonite, etc. D. (Sulfurous acid) Salt: calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, etc. E. Silicate: talc, clay, mica, asbestos, glass fiber, glass balloon, glass beads, calcium silicate, montmorillonite, bentonite, etc. F. Carbon: carbon black , Graphite, carbon fiber,
Carbon hollow spheres, etc. G. 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, etc. (2) Organic compounds Wood flour (pine, oak, sawdust, etc.), shell fiber (almond, peanut, fir shell, etc.), cotton, jute, paper strip , Cellophane pieces, nylon fibers, polypropylene fibers, starch, aromatic polyamide fibers, etc. Among these light-shielding substances, inorganic compounds that have excellent heat stability, are relatively inert to photographic light-sensitive materials, and have the ability to be opaque It is particularly preferable to use light-absorbing carbon black, titanium nitride, and graphite, which are relatively inert substances having excellent heat resistance and light resistance.

About 0.01% of lubricant is used to improve the handleability of photographic light-sensitive materials (ease of taking in and out of light-shielding bags), to improve extrusion suitability and film formability, to prevent static electricity and to prevent blocking.
It is preferably added in an amount of from about 1.0% by weight to about 1.0% by weight. In particular, it is essential to add it to a light-shielding polyolefin resin film.

The following are representative commercial lubricants and manufacturers that do not adversely affect the photographic film.

(1) silicone-based lubricant; various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Toray Silicone) etc. (2) Oleic amide lubricant; Armoslip CP (Lion Akzo), Neutron (Nippon Seika), Neutron E-18 (Nippon Seika), Amide O (Nitto Chemical), Alflo E-10 (Nippon Yushi),
Diamid O-200 (Nippon Kasei), Diamid G-2
00 (Nihon Kasei), etc. (3) Erucamide amide lubricant; Alflo-P-10 (Nippon Oil & Fats), etc. (4) Stearamide amide lubricant; Alflo-S-10 (Nippon Oil & Fats), Neutron 2 (Nihon Seiki) ), Diamid 200 bis (Nippon Kasei), etc. (5) Bis fatty acid amide-based lubricants; Bisamide (Nippon Kasei), Diamid 200 bis (Nippon Kasei), Armowax EBS (Lion Akzo), etc. (6) Alkylamine (7) hydrocarbon-based lubricant; liquid paraffin, natural paraffin, microwax, synthetic parifin, polyethylene wax, polypropylene wax, chlorinated hydrocarbon, fluorocarbon, etc. (8) ) fatty acid lubricants; higher fatty acids (C ₁₂ or higher is preferable), oxy fatty acid, etc. (9) ester lubricant; fatty acid lower Alcohol esters, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, etc. (10) Alcohol lubricants; polyhydric alcohols, polyglycols, polyglycerols, etc. (11) Metallic soaps; lauric acid, stearic acid , Ricinoleic acid, naphthenic acid, higher fatty acids such as oleic acid and Li, Mg, Ca, Sr, Ba,
It is preferable to add an antioxidant, such as a compound with a metal such as Zn, Cd, Al, Sn, and Pb, in order to prevent fish eyes from generating fish eyes and preventing coloring failure, and particularly to a light-shielding polyolefin resin film. It is essential to add. Representative examples of this antioxidant are shown below.

(A) phenolic antioxidant 6-t-butyl-3-methylphenyl derivative, 2.
6-di-t-butyl-P-cresol t-butylphenol), 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, alkylated bisphenol, styrenated phenol, 2,6-di- t-butyl-4-methylphenol, n-octadecyl-3-
(3'.5'-di-tert-butyl-4'-hydroxyphenyl) propinate, 2.2'-methylenebis (4-methyl-6-tert-butylphenol), 4.4'-thiobis (3-methyl- 6-t-butylphenyl), 4.4 ′
-Butylidenebis (3-methyl-6-t-butylphenol), stearyl-β (3.5-di-4-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-t-butyl-4'-hydroxyphenyl) propionate] methane and the like (ii) Ketone amine condensation antioxidant 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,4 -Polymers of trimethyl-1,2-dihydroquinoline, trimethyldihydroquinoline derivatives, etc. (c) Allylamine antioxidants 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-naphthylamine, etc. (d) Imidazole antioxidant 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, etc. E) Phosphite antioxidants Alkylated allyl phosphite, diphenylisodecyl phosphite, tris (nonylphenyl) phosphite sodium phosphite, trinonyl phenyl phosphite, triphenyl phosphite, etc. Inhibitors Thiourea derivatives, 1,3-bis (dimethylaminopropyl) -2-thiourea, etc. (G) Other antioxidants useful for air oxidation (H) Sulfur-based antioxidants Myristyl thiopropionate, lauri Stearyl thiodipropionate, systemic thiodipropionate Representative commercial antioxidants shown below.

(1) Phenolic antioxidants: SUMILIZER BHT (Sumitomo), IRGANOX1076 (Ciba Geigy), MARK AO-50 (ADEKA AUGUS), SUMILIZER B
P-76 (Sumitomo), TOMINOX SS (Yoshitomi), IRGANOX565 (Ciba Geigy), NONOX WSP (ICI), SANTONOX (Monsant
o), SUMILIZER WX R (Sumitomo), ANTAGECRYSTAL (Kawaguchi), IRGANOX1035 (Ciba Geigy), ANTGE W-400
(Kawaguchi), NOCLIZER NS-6 (Shinko Ouchi), IRGANOX1425
WL (Ciba Geigy), MARK AO-80 (Adeka Argus), SUMILIZER GA-80 (Sumitomo), TOPANOL CA (IC
I), MARK AO-30 (ADEKA Argus), MARK AO-20
(Adeka Argus), IRGANOX3114 (Ciba Geigy), MARK AO-330 (Adeka Argus), IRGANOX133
0 (Ciba Geigy), CYANOX1790 (ACC), IRGANOX1010
(Ciba Geigy), MARK AO-60 (Adeka Argus), SUMILIZER BP-101 (Sumitomo), TO-MINOX TT (Yoshitomi), etc. (2) Phosphorus antioxidants; IRGAFOS168 (Ciba Geigy), MARK2112 (Adeka Argus) , WESTON618 (Borg Warner), MARK PEP-
8 (Adeka Argus), ULTRANOX626 (Borg Warner), MARK PEP-24G (Adeka Argus), MARK PE
P-36 (Adeka Argus), HCA (Sanko), etc. (3) Thioether antioxidants; DLTDP “YOSHITOMI” (Yoshitomi), SUMILIZER TPL (Sumitomo), ANTIOX L (NOF), DMTD “YOSHITOMI” (Yoshitomi) ),
SUMILIZER TPM (Sumitomo), ANTIOX M (NOF), DSTP “YOS
HITOMI "(Yoshitomi), SUMILIZER TPS (Sumitomo), ANTIOX S
(NOF), SEENOX412S (Cipro), MARK AO-412S (Adeka Argus), SUMILIZER TP-D (Sumitomo), MARK A
O-23 (Adeka Argus), SANDSTAB P-EPQ (Sand), IRGAFOS P-EPQ FF (Ciba Geigy), IRGANOX12
22 (Ciba Geigy), MARK329K (Adeka Argus),
WES TON399 (Borg Warner), MARK260 (ADEKA
(Argus), MARK522A (Adeka Argus), etc. (4) Metal deactivator NAUGARD XL-1 (Uniroyal), MARK CDA-1 (Adeka Argus), MARK CDA-6 (Adeka Argus), LRGANOX MD- 1024 (Ciba Geigy), CUNOX (Mitsui Toatsu), etc. Particularly preferred antioxidants are phenolic antioxidants, and commercially available Irganox from Ciba Geigy are various types of Sumitomo Chemical's Sumilizer BHT and Sumilizer BH.
−76, Sumilizer WX-R, Sumilizer BP-101 and the like.

Also, 2.6-di-t-butyl-p-cresol (BH
T), low volatility high molecular weight phenolic antioxidants (trade names Irganox1010, Irganox1076, Topanol CA, Ionox330
1) such as dilauryl thiodipropionate, distearyl thiopropionate, dialkyl phosphate, etc.
It is effective to use two or more kinds, particularly two or more kinds in combination. It is preferable to use a phenolic antioxidant and a phosphorus antioxidant in combination, since the antioxidant effect becomes particularly excellent.

For example, when added to a polyolefin resin adhesive layer or a light-shielding polyolefin resin film,
0.003 to about 2.0% by weight.

If the amount is less than about 0.003% by weight, the effect of the addition is almost nil. On the other hand, if the amount of the additive exceeds about 2.0% by weight, the photographic film utilizing the oxidizing and reducing actions may be adversely affected and abnormal photographic performance may occur. For this reason, it is preferable to add the antioxidant in the minimum amount that does not cause coloring failure, spots, or fish eyes.

Further, when used in combination with carbon black or the like, the antioxidation exhibits a synergistic effect. In particular, it is preferable to use a phenol-based oxidizing waterproofing agent, carbon black, and a phosphorus-based antioxidant in combination, because the antioxidant effect is synergistically exhibited.

Other Antioxidants and Plastic Additives Data Collection (published by KK Chemical Industry Co., Ltd.) disclosed on pages 794 to 799 of the Plastic Data Handbook (published by the KK Industrial Research Committee)
Antioxidants and PLASTI disclosed on pages 327-329
It is possible to select and use various antioxidants disclosed on pages 211 to 212 of CS AGE ENCYCLOPEDIA Progress Edition 1986 (published by KK Plastic Age).

Next, typical examples of the additives will be described below, but the present invention is not limited thereto, and can be selected from all known ones.

The photographic light-sensitive materials to which the photographic light-sensitive material packaging material according to the present invention can be applied are shown below.

Silver halide photographic materials (X-ray films, printing films, color photographic papers, color films, printing master papers, DTR photographic materials, computer-printed films and papers, microfilms, movie films, self-developing photographic materials , Heat-developable photographic materials, direct positive films and papers, etc.) Diazonium photographic materials (4-morpholinobenzenediazonium chloride film, microfilms, copy films, printing plate materials, etc.) Azide, diazide photographic materials ( Photosensitive materials containing para-azide benzoate, 4.4 'diazide stilbene, etc.,
For example, copying films, printing plate materials, etc. Photosensitive materials containing quinonediazide-based photographic photosensitive materials (orthoquinonediazide, orthonaphthoquinonediazide-based compounds such as benzoquinone (1,2) -diazide- (2) -4-sulfonic acid phenyl ether) Materials, for example, printing plates, copying films, adhesion films, etc.) Photopolymers (photosensitive materials containing vinyl monomers, etc., printing plates, adhesion films, etc.), polyvinyl cinnamate esters (for example, printing films, (Resist for IC, etc.) [Function] In the packaging material for photographic light-sensitive material of the present invention, kraft paper having heat resistance and high Young's modulus has excellent bag-making suitability, appearance and curling, and suppresses external impact. As a result, pinholes and tears are less likely to occur in the inner light-shielding polyolefin resin adhesive layer. Aluminum deposited biaxially stretched thermoplastic resin film of the intermediate layer is light-shielding,
Moisture proof, gas barrier, antistatic, impact drilling strength,
It has excellent burst strength, and has excellent resistance to damage from outside and inside and damage by objects having sharp edges. Since the light-shielding polyolefin-based resin adhesive layer is a thin layer, there is no curling, and the tear strength is increased while maintaining the notch effect. In addition, since the light-shielding polyolefin-based resin film contains carbon black that absorbs light, it prevents light penetration due to the piping effect from the cross-section and poor light-shielding properties due to the generation of pinholes. Improves heat seal suitability.

〔Example〕

An embodiment of the packaging material for a photographic light-sensitive material of the present invention will be described with reference to FIGS.

1 to 8 are partial sectional views showing the layer structure of the packaging material for photographic light-sensitive materials.

The packaging material for photographic light-sensitive materials shown in FIG. 1 has a biaxially stretched thermoplastic resin film 1 on which an aluminum vapor deposition film 2 is vapor-deposited on the side of the biaxially stretched thermoplastic resin film 1 of the aluminum vapor deposited biaxially stretched thermoplastic resin film I. A light-shielding polyolefin-based resin film 5a is laminated via the adhesive layer 3,
6 is laminated on the aluminum-deposited biaxially stretched thermoplastic resin film I on the aluminum-deposited film 2 side via a light-shielding polyolefin-based resin adhesive layer 4a.

The packaging material for photographic photosensitive material shown in FIG. 2 is an aluminum-deposited biaxially-stretched thermoplastic resin film Ia obtained by depositing an aluminum-deposited film 2 on a biaxially-stretched thermoplastic resin film 1a containing a light-shielding substance. The light-shielding polyolefin resin film 5a is laminated via an adhesive layer 3a containing a light-shielding substance on the side of the aluminum-evaporated biaxially stretched thermoplastic resin film Ia on the side of the biaxially stretched thermoplastic resin film 1a. Light-shielding polyolefin resin adhesive layer
6 are stacked via 4a.

The packaging material for photographic light-sensitive material shown in FIG. 3 is a light-shielding polyolefin-based resin film 5a directly on the aluminum-deposited biaxially stretched thermoplastic resin film I side of the aluminum-deposited film 2 side.
The kraft paper 6 is laminated on the aluminum-evaporated biaxially stretched thermoplastic resin film I on the side of the biaxially stretched thermoplastic resin film 1 via the light-shielding polyolefin resin adhesive layer 4a.

The packaging material for photographic light-sensitive material shown in FIG. 4 is a light-shielding thermoplastic resin film 7a on the side of the biaxially stretched thermoplastic resin film 1 of the aluminum-deposited biaxially stretched thermoplastic resin film 1 via an adhesive layer 3. Light-shielding polyolefin resin film 5a and a light-shielding polyolefin-based resin film 5a are laminated, and a light-shielding polyolefin-based resin adhesive layer is provided on the aluminum-deposited biaxially stretched thermoplastic resin film I side of the aluminum-deposited film 2. Kraft paper is laminated through 4a.

The packaging material for a photographic light-sensitive material shown in FIG. 5 has two layers of a light-shielding polyolefin resin adhesive layer in the layer configuration shown in FIG.
A two-layer co-extruded light-shielding polyolefin resin adhesive layer IIIa composed of 4a and 4a is used.

The packaging material for photographic light-sensitive material shown in FIG. 6 is a thermoplastic resin containing no light-shielding substance in place of the light-shielding thermoplastic resin film 7a of the light-shielding multilayer coextruded polyolefin resin film IIa in the layer constitution of FIG. Instead of the resin film 7 and the adhesive layer 3, an adhesive layer 3a containing a light-shielding substance is used.

The packaging material for photographic light-sensitive material in FIG. 7 is a two-layer co-extruded film of light-shielding polyolefin resin films 5a and 5a in place of the light-shielding multilayer co-extruded polyolefin resin film IIa in the layer configuration of FIG. The blocking light-shielding multilayer co-extruded polyolefin resin film IVa is laminated on the light-shielding multilayer co-extruded polyolefin resin film IIa.

The packaging material for photographic light-sensitive material shown in FIG. 8 has a light-shielding polyolefin resin film 5a and a light-shielding thermoplastic resin film 7a in place of the light-shielding multilayer co-extruded polyolefin resin film IIa in the layer constitution shown in FIG. Light-shielding multilayer co-extruded polyolefin resin film IIa comprising
Blocking adhesive light-shielding multilayer coextruded polyolefin resin film IVa in which IIa is blocked and bonded between light-shielding thermoplastic resin films 7a, 7a is laminated.

Although various known adhesive layers can be used as the adhesive layer 3, it is preferable to use a polyolefin resin adhesive layer that can be tandem-laminated and has a low lamination cost. In addition, the thermoplastic resin film 7 or
Although various thermoplastic resin films can be used as 7a, it is preferable to use a polyolefin-based resin film in view of physical strength, film formability, cost, and the like.

 Next, the experimental results of the products I and II of the present invention will be described.

The product I layer structure of the invention corresponds to FIG.

Kraft paper 6 contains aluminum sulfate and polyacrylamide, but chlorine, propylene oxide,
Unbleached kraft paper with a Young's modulus of 428 kg / mm ² and a basis weight of 50 g / m ² that does not contain substances that adversely affect photographic light-sensitive materials such as ethylene oxide.

The light-shielding polyolefin resin adhesive layer 4a has a MI containing 3% by weight of carbon black of 5.1 g / 10 minutes and a density of 0.9.
An extrusion LDPE resin adhesive layer of 19 g / cm ^{3 and} a thickness of 20 μm was used in tandem lamination with an LDPE resin adhesive layer described later.

Aluminum deposited biaxially stretched thermoplastic resin film I
Is a biaxially stretched thermoplastic resin film 1 having a thickness of 15 μm.
Using a biaxially stretched nylon resin film with a thickness of 40
An aluminum vacuum-deposited biaxially stretched nylon film obtained by vacuum-depositing a 0 ° aluminum deposited film 2 was used.

The adhesive layer 3 has a MI of 15 μm in thickness of 5.1 g / 10 minutes and a density of
An LDPE resin adhesive layer of 0.919 g / cm ³ was used. The light-shielding multilayer co-extruded polyolefin resin film IIa has a MI of 1.1 g / 10 minutes and a density of as light-shielding thermoplastic resin film 7a.
0.954 g / cm ³ HDPE resin 20 wt%, MI 2.1 g / 10 min, density 0.920 g / cm ³ ethylene / 4 methylpentene-1 copolymer resin 72.25 wt%, MI 2.4 g / 10 min , Density is 0.926g / cm ³
4.5% by weight of LDPE resin, furnace carbon black 3
40% by weight of a composition consisting of 0.1% by weight of LDPE resin masterbatch containing 40% by weight of carbon black, 0.1% by weight of synthetic silica, 0.05% by weight of erucamide, and 0.1% by weight of phenolic antioxidant MI as a light-shielding polyolefin resin film 5a
2.1 g / 10 min, density of 0.920 g / cm ³ ethylene / 4-methylpentene-1 copolymer resin 92.25 wt%, MI 2.4 g / 10 min,
4.5% by weight of LDPE resin with a density of 0.926 g / cm ³ , furnace carbon black (7.5% by weight of LDPE resin masterbatch containing 40% by weight of furnace carbon black)
3% by weight, synthetic silica 0.1% by weight, erucamide 0.05
A light-shielding two-layer co-extruded blown film having a thickness of 80 μm was prepared using a film having a thickness of 40 μm and a composition of 0.1% by weight of a phenolic antioxidant.

Using the laminated film described above, a bottom heat seal width of 10
A single gazette bag with a width of 89 mm and a length of 180 m was printed and hermetically sealed. As a result, pinholes and bag breaks did not occur even if the conventional bottom portion was not bent and fixed with an adhesive.

FIG. 8 shows the layer structure of the product II of the present invention.

Kraft paper 6, light-shielding polyolefin resin adhesive layer
4a, the aluminum-deposited biaxially stretched thermoplastic resin film I and the adhesive layer 3 are the same as the product I of the present invention.

The blocking adhesive light-shielding multi-layer coextruded polyolefin resin film IVa is a 20 μm thick film having the same resin composition as the light-shielding thermoplastic resin film 7a of the product I of the present invention as the outer light-shielding polyolefin resin film 5a. As the inner light-shielding polyolefin-based resin film 7a, MI of 2.1 g / 10 minutes and a density of 0.920 g / cm ³ of ethylene
84.5% by weight of 4-methylpentene-1 copolymer resin, MI of 0.
4 g / 10 min, density 0.900 g / cm ³ , molecular weight distribution 8.3 ethylene / butene-1 copolymer resin 12.3% by weight, furnace carbon black 3% by weight, silica 0.1% by weight, oleic acid amide 0.05% by weight, Phenolic antioxidant 40 thickness using a 20 μm thick film composed of 0.15% by weight
It is a blocking-adhesive light-shielding multi-layer coextruded polyolefin resin film having a thickness of 80 μm in which a 5 μm, 7a light-shielding two-layer co-extruded blown film of 7 μm is blocked and bonded between 7a, 7a using a nip roll.

Using the laminated film described above, a single gusset bag similar to the product I of the present invention was prepared, and a color photographic paper was hermetically packaged. As a result, similar to the product I of the present invention, no pinhole or bag break occurred.

〔The invention's effect〕

Since the present invention is configured as described above, the light-shielding polyolefin resin adhesive layer is hardly damaged by impact or sharp edges, the light-shielding layer can be formed by a tandem lamination method, inexpensive, durable, and charged. It is a packaging material with excellent prevention and light-shielding properties.

[Brief description of the drawings]

1 to 8 are partial cross-sectional views showing the layer structure of an embodiment of the packaging material for a photographic light-sensitive material of the present invention. 1, 1a ...... biaxially oriented thermoplastic resin film 2 ...... aluminum deposited layer 3, 3a ...... adhesive layer 4, 4a _1, 4a ₂ ...... light-shielding polyolefin resin adhesive layer 5a ...... light-shielding polyolefin Resin film 6, 6a: Kraft paper 7, 7a: Thermoplastic resin film I, Ia: Aluminum vapor-deposited biaxially stretched thermoplastic resin film IIa: Light-shielding multilayer co-extruded polyolefin resin film IVa: Blocking Adhesive light-shielding multi-layer coextruded polyolefin resin film a. B: Indicates blocking adhesion.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-18547 (JP, A) JP-A-63-99254 (JP, A) JP-A-63-286344 (JP, A) 141729 (JP, U) JP-A 63-105142 (JP, U) JPO Bulletin 53-219 [2568] Well-known and conventional technology collection (packaging industry) Published December 20, 1978, p.499

Claims (2)

(57) [Claims] 1. An aluminum-evaporated biaxially stretched thermoplastic resin film, laminated on one surface of the thermoplastic resin film, having a melt index of 0.8 to 10 g / 10 minutes and a density of 0.870.
A light-shielding polyolefin-based resin film containing, as a main component, an ethylene / α-olefin copolymer resin of about 0.940 g / cm ³ and further containing carbon black, an antiblocking substance, 0.003 to 2.0% by weight of an antioxidant, and a lubricant; A kraft paper laminated on the other surface of the plastic resin film via a light-shielding polyolefin-based resin adhesive layer, the packaging material for a photographic photosensitive material used for a single gusset bag. (2) The carbon black has a pH of 6.0 to 8.5,
Average particle size is 15 ~ 50μm, volatile content is 3% or less, oil absorption
2. A packaging material for a photographic light-sensitive material according to claim 1, which is acetylene carbon black or furnace carbon black of 60 cc / 100 g or more.