JPH04190230A - Packaging material for photosensitive material - Google Patents

Abstract

PURPOSE:To provide a material having good film moulding property, bag making property, and other various properties to be further improved by providing a light shielding polyolefine resin layer including a specified quantity of resin selected among ethylene, alpha-olefine copolymeric resin, carbon black, etc. CONSTITUTION:A packaging material having a light shielding polyolefine resin layer including 5 - 90wt% resin consisting more than one selected among ethylene, alpha-olefine copolymeric resin, carbon black, etc., comprises a single layer film comprising a light shielding polyolefine resin layer 1a only, a two-layer extrusion inflation film 3a comprising the resin layer 1a laminated with a light reflecting light shielding layer 2a, and a flexible sheet layer 5 laminated through a layer 4 of binding agent. The sheet layer 5 is laminated with the light shielding layer 2a of the film 3a as a subject material through the layer 4. The resin layers 1a, 1a laminated on both sides of the subject material and the sheet layer 5 through the layers 4, 4, thereby many conflicting properties such as a physical strength, heat seal property, etc., required for a photosensitive material packaging material can thus be good.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to packaging materials for photosensitive materials, in particular for photographic materials.

[Conventional technology]

Conventionally, as packaging materials for photosensitive materials, light-shielding LDPR resin film layers containing carbon black or light-shielding HD
Although some have a PE resin film layer, these have low physical strength, lack heat sealability, and have various drawbacks as packaging materials for photosensitive materials.

In addition, as a packaging material that improves the physical strength of the above-mentioned packaging materials, we have developed a layer of low-pressure normal low-density polyethylene (hereinafter referred to as L-LDPE) resin of 50% or more by weight, and a light-shielding polyethylene containing carbon black. There are packaging materials comprising a polyolefin polymer film layer and a multilayer coextruded blown film containing an L-LDPE resin film layer and a polyolefin resin film (Japanese Patent Publication No. 2-2700 and Japanese Patent Application Laid-open No. 1999-1-1999). 195
No. 042).

[Problem to be solved by the invention]

However, the above-mentioned packaging material equipped with a light-shielding polyethylene polymer film layer or a packaging material made of a multilayer coextruded blown film comprising an L-LDPH resin layer and a light-shielding polyethylene polymer film layer has excellent physical strength. However, film formability,
It was necessary to further improve the drip-proofing properties, antistatic properties, heat-sealability over a wide temperature range, hot-tack properties, and suitability for high-speed bag making of light-shielding and sealed bags.

The present invention solves the above problems and provides a packaging material for photosensitive materials that maintains the convenient properties of conventional packaging materials such as physical strength, while improving film formability, bag-making suitability, use suitability, appearance, etc. The purpose of the present invention is to provide a packaging material for photosensitive materials that is excellent in various properties that should be further improved.

[Means to solve the problem]

The packaging material for photosensitive materials of the present invention comprises ethylene/α-olefin copolymer resin, carbon black, fatty acid amide or silicone, surfactant, antioxidant, homopolyethylene resin, ethylene/vinyl acetate copolymer resin, and ethylene-vinyl acetate copolymer resin. The present invention is characterized by comprising a light-shielding polyolefin resin layer containing 5 to 90 percent by weight of one or more resins selected from ethyl acrylate copolymer resins.

Ethylene/α-olefin copolymer resin has a narrow molecular weight distribution, is linear, and is manufactured using a low-pressure process that is inexpensive compared to LDPE resin that is manufactured using a conventional high-pressure process (3000 atm, 300'C). Energy-saving process products can be used.

Manufacturing methods include a gas phase method, a liquid phase method, and a high pressure modification method using ionic polymerization.

Preferred typical ethylene/α-olefin copolymer resins include ethylene and butene-1 (carbon number 4).
L-LDPE resin, copolymerization of ethylene and hexene-1 (α-olefin with 6 carbon atoms) L-LDPE resin, ethylene and 4-methylpentene-1
1 (α-olefin with 6 carbon atoms) copolymerized L-LDPE
There is L-LDPE resin, which is a copolymer of ethylene and octene-1 (α-olefin having 8 carbon atoms).

Specific trade names of these resins and their manufacturing methods are shown below.

a: Copolymerization of ethylene and butene-1 L-LDPE resin Vapor phase method: G resin or Unipol (Union Carbide), NUC polyethylene-LL (Nippon Unicar), etc. Liquid phase method: Idemitsu Polyethylene L (Idemitsu) petrochemistry)
, Nirex (Japan Petrochemical), Sflare (DuPont Canada), etc. High pressure modification method (ionic polymerization method)...Rotrex (CDF Chi)
ie) etc. b: Copolymerization of ethylene and hexene-1 L-L
DPE resin vapor phase method...TUFULIN (Union Carbide) etc. C: Ethylene and 4-methylpentene-1
Copolymerization of L-LDPE resin liquid phase method...Urtzex (Mitsui Petrochemical) etc. d: Copolymerization of ethylene and octene-1 L-LDPE resin liquid phase method...Stamilex (DSM-Stamicarbon) ,
Carbon blacks such as Dowlex (Dow Chemical Company) and MORETEC (Idemitsu Petrochemicals) are categorized by raw materials: gas black, furnace black, channel black, anthracene black, acetylene black, Ketschene carbon black, thermal black, lamp black,
There are oil smoke, powder smoke, animal black, vegetable black, etc.

The carbon black contains 90% of one or more selected from furnace carbon black and acetylene carbon black in terms of the balance of light-shielding properties, heat-sealing properties, physical strength, photographic properties, and moldability, and
Preferably 0.1 to 20 of the light-shielding polyolefin resin layer
Preferably it accounts for % by weight, particularly preferably from 0.5 to 10% by weight, most preferably from 1.0 to 5.0% by weight.

The forms in which carbon black is blended can be roughly classified as follows.

(1) Uniformly colored pellets (the most commonly used type is called color compound) (2) Dispersible powder (also called dry color, treated with various surface treatment agents and further treated with dispersion aids) (3) Paste (dispersed in plasticizer, etc.) (4) Liquid (liquid, also called liquid color, dispersed in surfactant, etc.) (5) Masterbatch pellet form (carbon black dispersed at a high concentration in the plastic to be colored) (6) Moisturizing granular powder form (carbon black dispersed at a high concentration in the plastic and then processed into a granular powder form) (7) Dry powder form (ordinary untreated dry powder form) There are various forms of blending carbon black as mentioned above, but the masterbatch method is preferred in terms of cost, prevention of contamination of the workplace, etc. preferable. Japanese Patent Publication No. 40-26196, a known document, describes a method for preparing a polymer-carbon black masterbatch by dispersing carbon black in a solution of a polymer dissolved in an organic solvent; It describes a method for making a masterbatch by dispersing black in polyethylene.

Fatty acid amide or silicone is limited to a lubricant that effectively exhibits resin fluidity, moldability, packaging workability (suitability for bag making, suitability for loading and unloading photosensitive materials), and anti-blocking properties, and fatty acids, fatty acid metal salts, and fatty acid esters. , antistatic agents, and higher alcohols are not allowed. This fatty acid amide or silicon bleeds out to the surface in a very short time immediately after molding and improves the above properties, but on the other hand, it may deteriorate heat sealing properties and anti-blocking properties, and may adhere to photographic materials during development. This causes various problems such as obstruction and adhesion of the resulting white powder to products. Therefore, when used in packaging materials for photosensitive materials, the amount added is preferably 0.5% by weight or less, particularly preferably 0.2% by weight or less, and most preferably 0.
．． By limiting the amount to 1% by weight or less and using it in combination with carbon black, surfactant, and ethylene/α-olefin copolymer resin, the above problems can be solved, and synergistic effects can be achieved on antistatic properties, moldability, and packaging workability. Make it effective.

As the fatty acid amide, for example, those described below are preferable.

(1) Oleic acid amide lubricant; Armorip CP (
Lion, Akzo), Neutron (Nippon Sakka), Neutron E-18 (Nippon Sakka), Amide 0 (Nitto Chemical)
, Alflo E-10 (NOF), Diamond 0-2
00 (Nippon Kasei), Diamond G-200 (Nippon Kasei), etc. (2) Erucic acid amide lubricant; Alflo P-10 (NOF), etc. (3) Stearic acid amide lubricant; Alflo S-10
(NOF), Neutron 2 (Nippon Rukka), Diamond 200 (Nippon Kasei), etc. (4) Bis fatty acid amide lubricants; Bisamide (Nippon Kasei), Diamond 200 Bis (Nippon Kasei), Armowax EBS (Lion Akzo) ) and other silicones include dimethylpolysiloxane, carboxyl-modified silicone oil, etc. (Shin-Etsu Chemical, Toshiba Silicone, Toshi Silicone,
Union Cardide, Dow Corni
ng, etc.).

In particular, linear polydimethylsiloxane having a viscosity of 1,000 to 60,000 cs is preferred, since it does not adversely affect photographic materials such as fogging.

Examples of surfactants include those shown below.

■Nonionic surfactants (typical ingredients polyoxyethylene glycols) ■Anionic surfactants (typical ingredients sulfonates) ■Cationic surfactants (typical ingredients quaternary ammonium salts) ■Ampholytic surfactants Representative examples of the above nonionic surfactants are shown below.

Polyethylene glycol fatty acid ester polyoxyethylene sorbitan fatty ester polyoxyethylene fatty alcohol ethyl polyoxyethylene glycerin fatty acid ester polyoxyethylene fatty amine sorbitan monofatty acid ester fatty acid pentaerythrite ethylene oxide adduct of fatty alcohol ethylene oxide adduct of fatty acid Ethylene oxide adducts, ethylene oxide adducts of alkylnaphthols, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, and various other nonionic surfactants described in Japanese Patent Publication No. 63-26697, page 120.

Representative examples of anionic surfactants are shown below.

Wasylic acid sulfate ester soda salt Various fatty acid metal salts Wasylic acid ester sulfate ester soda salt Sulfated oleate Ethyl aniline Olefin sulfate ester salt Oleyl alcohol sulfate ester Sodium salt Alkyl sulfate ester salt Fatty acid ethyl sulfonate Alkyl sulfonate Alkylnaphthalene sulfone Acid salts, alkylbenzene sulfonates, succinate esters, sulfonates, phosphate ester salts, etc.

The cationic surfactants are shown below.

Primary amino salt Tertiary amine salt Quaternary ammonium salt Pyridine derivatives etc.

Representative examples of amphoteric surfactants are shown below.

carboxylic acid derivatives imidacillin derivatives Betaine derivatives, etc.

The above surfactants are preferably added in an amount of 0.01 to 5% by weight, particularly preferably 0.1 to 3% by weight, and most preferably 0.2 to 1% by weight.

Antioxidants are added to prevent spots caused by resin burning. Phenol type and phosphate type are preferable from the viewpoint of photographic properties, and it is better to use two types in combination than one type. In the present invention, the addition of carbon black is an essential requirement, and due to the synergistic effect with the antioxidant effect of carbon black, it is sufficient to add the antioxidant in an amount of 0.5% by weight or less, preferably 0.2% by weight. It is as follows. Since it has an adverse effect on photographic materials that utilize redox action, it is preferable that the amount added be small.

It is preferable that at least one of a phenolic antioxidant and a phosphate antioxidant is added to the resin composition of the present invention. These antioxidants are used to prevent coloring failure of the resin when the resin temperature is increased. Antioxidants other than phenol-based and phosphate-based antioxidants are undesirable because they have an adverse effect on the photosensitive material, so when added, the 0.
It should be less than 2% by weight.

Examples of phenolic antioxidants include those listed below.

■n-octadecyl-3(3'',5'-di-t-butyl 4'hydroxyphenyl)propinate ■2,6-di-t-butyl 4-methylphenol ■2,6
Di-t-butyl-p-cresol ■2,2"-methylenebis(4-methyl-6-t-butylphenol) ■4.4"-thiobis(3-methyl-6-t-butylphenol) ■4,4"- Butylidene bis(3-methyl-6-t-butylphenol) ■Stearyl β(3,5-di-4-butyl-4-hydroxyphenyl)propionate ■1,1.3-tris(2-methyl-4-hydroxy-5- t-Butylphenyl)butane [phase] 1,3.5-trimethyl-2,4,6,-)lis(3,5-di-t-butyl-4-hydroxybenzyl)benzene Tetrakis[methylene-3( 3', 5'-
Commercially available products of di-[-butyl-4”-hydroxyphenyl)propionate comethane include Ciba Geigy's Irganox and Sumilizer B from Jujutsu Kagaku.
HT, SumilizerBP-76, Sumiliz
There are products such as WX-R+Sumilizer BP-101.

Examples of phosphate antioxidants include those listed below.

Trinonylphenylphosphate Triphenylphosphate In the present invention, since it is used in combination with carbon black, the antioxidant effect is synergistically improved. Furthermore, since it is colored black, the blackish-brown coloration caused by resin burnout does not become a problem due to the total heat.

As an example of a high-pressure branched low-density homopolyethylene (LDPE) resin, which is the most preferred among homopolyethylene resins, the product name and resin manufacturer commercially available in Japan are listed below.

Manufacturer Salt Product Name Sumitomo Chemical
Sumikasen Mitsubishi Yuka Yucalon Mitsui Petrochemical Mirason Nippon Unicar NUC Polyethylene Ube Industries
UBE Polyethylene Nippon Petrochemical
Kusuron Toyoso Petrosen Showa Denko Showa Denko Showlex Mitsubishi Kasei
Tubatic-L Asahi Kasei Santic-LD ethylene/vinyl acetate copolymer resins include the following products from the following manufacturers.

Manufacturer salt product name Showa Denko
Shorex EVA Sumitomo Chemical
Evatate Toyo Thor Ultrasen Mitsui Petrochemical Mirason EVA Nippon Unicar
As the NUCEVA copolymer ethylene-ethyl acrylate copolymer resin, there are the following products from the following manufacturers.

Manufacturer Salt Product Name Nippon Unicar NtlCEV Hachihe Polymer Mitsui DuPont Polychemical Evaflex EEA
One or more resins selected from the above three resins are 5
Contains ~90% by weight. If it is less than 5% by weight,
The effect of improving film formability, bag making suitability, appearance, and productivity is small.

Moreover, if it exceeds 90% by weight, physical strength decreases, and heat sealability (hot tack property, impurity sealing property, heat seal strength, etc.) deteriorates.

Moreover, an antiblocking agent can be added to the light-shielding polyolefin resin layer in order to prevent blocking.

Anti-blocking agents include silica, diatomaceous earth, talc, calcium silicate, aluminum silicate, magnesium silicate, calcium carbonate, higher fatty acid polyvinyl ester, n-octadecyl urea, dicarboxylic acid ester amide, N, N'-dioley, oxamide, carbonic acid. Zeolite or the like with calcium deposited on its surface is used. Since it is used in combination with carbon black, fatty acid amide, and surfactant, it has good dispersibility, reduces the occurrence of lumps, and improves the anti-blocking effect.

Such an antiblocking agent is preferably 0.01
-10% by weight, particularly preferably 0.5-3% by weight.

Further, the light-shielding polyolefin resin layer of the present invention may be formed by coextrusion;
20% by weight of HDPE resin with a density of 0.954g/cffl at /10 minutes, the old has a density of 0.92 at 2.1g/10 minutes
Thickness consisting of 73.5% by weight of ethylene/4-methylpentene-1 copolymer resin of 0 g/cTI, % of titanium oxide, 0.05% by weight of oleic acid amide, and 0.45% by weight of stearic acid monoglyceride. A two-layer coextruded blown film may be obtained by coextruding with a 40nr light-reflecting light-blocking layer.

Further, various flexible sheets may be laminated on the light-shielding polyolefin resin layer of the present invention. Examples of the flexible sheet layer include aluminum vacuum-deposited biaxially stretched thermoplastic resin film, metal foil, various papers, nonwoven fabrics, synthetic papers, and the like. It is preferable that this flexible sheet layer has a melting point higher than that of the light-shielding polyolefin resin layer by 10° C. or more from the viewpoint of improving bag-making suitability.

The packaging material for photosensitive materials of the present invention can be used for packaging various products, particularly silver halide photographic materials, diazo photographic materials, photosensitive resins, self-developing photographic materials, and diffusion transfer photographic materials. It is ideal as a packaging material for direct positive photosensitive materials, etc. Others: light, static electricity,
It can be used for packaging products such as foodstuffs, pharmaceuticals, chemicals, and ICs whose quality is destroyed or degraded by dust or the like.

When the packaging material of the present invention is applied to, for example, the above-mentioned photosensitive materials, its usage forms include - vertical flat bags, double flat bags, heavy gusset bags, double gusset bags, laminated films, packaging bags for loading in bright rooms, A sheet-like or tube-like antistatic light-shielding film for wrapping a roll of photosensitive material can be considered, and all other known forms can be used.

[Effect]

In the packaging material for photosensitive materials of the present invention, the ethylene/α-olefin copolymer resin improves physical strength and heat-sealing suitability (particularly heat-sealing strength over time, hot tack property, and contaminant sealing property). Fatty acid amide or silicone effectively exhibits resin fluidity, moldability, carbon black dispersibility, packaging workability (bag-making ease, ability to put in and take out photosensitive materials), and anti-blocking properties. Surfactants improve antistatic properties, drip-proof properties, white powder prevention properties, and carbon black dispersibility. Antioxidants prevent clumping and improve film formability. The synergistic effect of using carbon black, fatty acid amide or silicone, surfactants, and antioxidants significantly reduces the generation of white powder and scum due to bleed-out, while providing antistatic and drip-proof properties. Improves antioxidation properties, antioxidation properties, and antiblocking properties. One or more resins selected from homopolyethylene resins, ethylene-vinyl acetate copolymer resins, and ethylene-ethyl acrylate copolymer resins exhibit heat-sealing strength and hot tack properties over a wide temperature range, and can improve fluidity by improving fluidity. It is possible to ensure heat-sealing strength over time and low-temperature heat-sealability, and also prevent pinballing from occurring during heat-sealing.

〔Example〕

Examples of the packaging material for photosensitive materials of the present invention will be described based on FIGS. 1 to 5.

1 to 5 are partial cross-sectional views showing the layer structure of an embodiment of the packaging material for photosensitive materials of the present invention.

The packaging material for photosensitive materials shown in FIG. 1 is a single-layer film consisting only of a light-shielding polyolefin resin layer 1a.

The packaging material for photosensitive materials shown in FIG. 2 is a two-layer coextruded blown film 3a in which a light-reflecting light-shielding layer 2a is laminated on a light-shielding polyolefin resin ff1IB.

In the packaging material for photosensitive materials shown in FIG. 3, a flexible sheet layer 5 is laminated on a light-shielding polyolefin resin layer 1a via an adhesive N4.

The packaging material for photosensitive materials shown in FIG. 4 has a light-reflecting light-shielding layer 2a of the same two-layer coextruded blown film 3a as shown in FIG. Laminated.

In the packaging material for photosensitive materials shown in FIG. 5, light-shielding polyolefin resin layers 1a and 1a are laminated on both sides of a flexible sheet layer 5 via adhesives N4 and 4, respectively.

Next, the results of an experiment comparing the characteristics of products 1 to 16 of the present invention and comparison products 1 to 8 are shown in Tables 1, 2, and 3 along with their structures. These films were all produced by a blow-up film molding method using a ring die with a die slit of 1 mm, using an air cooling method at a blow-up ratio of 1.5. The thickness of the film is 80
It was set as r.

(Margin below) The various resins in the table are as follows.

A: Ethylene/α-olefin resin Al: Ethylene/4-methylpentene-1 copolymer resin M
12. Og/10 min, density 0.920g/cfflA2
:Ethylene/octene-1 copolymer resin M12.4g/
10 minutes, density 0.923 g/c [IYB; homopolyethylene resin B1: high pressure branched low density homopolyethylene resin M12
．． 6g/10min, density 0.926g/cfflB2: Low pressure method linear high density homopolyethylene resin gate If, 2g/cffl
10 minutes, density 0.950g/cfflC; ethylene ethyl acrylate resin C+: M16. Og/10min, density 0.930g/c
JD; ethylene vinyl acetate copolymer resin D, :MI2. Ig/10 min, density 0.921g
/cI+! 1 for surfactant, 2 for stearic acid monoglyceride, 2 for polyoxyethylene nonylphenol ether S; antioxidant S, 2-6-di-t-butyl-para-cresol (BI
T) S2: Tetrakis [methylene-3(3',5'-di-L-butyl-4''-hydroxyphenyl)propionate comethane Evaluation is as follows.

◎...Excellent ○...Excellent...Possible (within practical limits) Mu...Problems in practical application (improvement required) ×...Not practical for films in the table The characteristics test method is as follows.

B: Preventing the formation of lumps (clumps) When each sample is made using a blown film molding machine, the degree of difficulty in forming lumps is determined by visual inspection of the film appearance; Preventing the formation of white powder: After being left in a heated room at 35°C for 4 weeks,
Determine the degree of white powder generated on the surface of the film by visual inspection; Prevention of water droplets A roll of photographic film is sealed in a bag made using the packaging material of the present invention and stored in a low temperature warehouse at 10°C for 5 days. After being stored for 1 day, the bag was left in a room at 20°C and 60% RH for 10 minutes, and the amount of water droplets adhering to the front and back of the sealed bag was visually inspected. rear,
After being stored in a storage room at room temperature for 5 days after being wound into a roll, judgment is made based on the state of blocking when unrolling; Anti-static properties Each film to be tested has a width of 35 mm and a length of 1350 m.
Make an endless belt of m and load this belt with 500
The evaluation was based on the peeling voltage measured with a voltmeter when the film was fed between the SUS roller (made of stainless steel) and the SOS roller at a speed of 12 m/min; Film formability The motor load when forming the blown film ( current value), bubble stability, frost line position,
Evaluated based on total blown film manufacturing suitability such as fish eyes, film wrinkles, and unevenness in film thickness; heat sealability heat seal strength, hot tack property 4, contaminant sealability, sheet seal strength over time, heat sealable allowable temperature, etc. Judging from the total heat-sealing suitability of packaging processing suitability Evaluated from the ease of work when sealing and packaging a roll of photographic film in a bag made using the packaging material of the present invention [Effects of the invention] Photosensitive of the present invention The packaging material for the material was constructed as described above, so it has excellent physical strength, heat sealability (low temperature heat sealability, hot tack property, heat sealable temperature range, heat seal strength over time, pinhole prevention property, etc.), and film forming properties. It has many contradictory properties required as a packaging material for photosensitive materials, such as anti-blocking properties, antistatic properties, anti-blocking properties, anti-white powder properties, light-shielding properties, anti-water drop properties, and suitability for packaging processing.

[Brief explanation of drawings]

1 to 5 are partial cross-sectional views showing the layer structure of an embodiment of the packaging material for photosensitive materials of the present invention. 1a... Light-shielding polyolefin resin layer 2a... Light-reflective light-shielding layer 4... Adhesive layer 5... Flexible sheet layer a... Patent applicant indicating that it contains a light-shielding substance Fuji Photo Film Co., Ltd. Agent Patent Attorney Seiji Tanaka 1 person 1st cause Ward 2 Figure 3 Figure 4 Figure 5

Claims (2)

[Claims] (1) Ethylene/α-olefin copolymer resin, carbon black, fatty acid amide or silicone, surfactant, antioxidant, homopolyethylene resin, ethylene/vinyl acetate copolymer resin, and ethylene-ethyl acrylate copolymer resin. 5~ consisting of 1 or more selected from among
A packaging material for photosensitive materials, characterized by comprising a light-shielding polyolefin resin layer containing 90% by weight of resin. (2) A packaging material for photosensitive materials, characterized in that the light-shielding polyolefin resin layer according to claim (1) is the innermost layer, and the flexible sheet layer is laminated as the outermost layer.