JPH04149542A - Packing bag for keeping print for a long time and method for keeping print for a long time using it - Google Patents

Abstract

PURPOSE:To prevent the deterioration of a printed image for a long time, which is equal to or more than ten years, even under the condition of an ordinary home by forming an innermost layer of mildewproof polyolefine resin layer in which the total amount of mildewed substance is equal to or under a specified value and ethylene copolymer resin equal to or above a specified value is contained. CONSTITUTION:The innermost layer is the mildewproof polyolefine resin film in which the total amount of mildewed substance is <=5 wt.%, and >=5 wt.% ethylene copolymer resin is contained. The mildewed substance is starch, various kinds of fatty acid, and various kinds of lubricant. It is desirable to add a mildewproofing agent and perform disinfection treatment simultaneously, and the addition amount of the mildewproofing agent is 1-1000ppm, desirably, 5-200ppm. The ethylene copolymer resin contained in the mildewproof polyolefine resin layer is ethylene.alpha-olefine copolymer resin, and ethylene.acrylic acid copolymer resin, and it is good to singly use the ethylene copolymer resin or mix and use two or more kinds of ethylene copolymer resin. The ethylene.alpha-olefine copolymer resin by a low pressure method and the ethylene.acrylic acid ethyl copolymer resin, which are excellent in heat sealing characteristic and physical strength, are desirable among them.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a light-shielding bag suitable for preventing image deterioration of prints, particularly photographic prints, and a method for long-term preservation of prints using this light-shielding bag. .

[Conventional technology]

Image information, especially photographic images, is extremely superior in terms of the amount, accuracy, and permanence of information, and thus, along with documents, it has become a means of transmitting modern society to future generations.

However, since photographic materials are a composite of organic and inorganic materials, image deterioration is a constant problem, and for long-term preservation, it is essential to make the images more robust and develop preservation techniques.

The deterioration of prints (images) can be broadly classified into: ■biological, ■physical, and chemical and photochemical deterioration.

Biological deterioration is particularly likely to occur in the daily living environment of ordinary households, and when the relative humidity exceeds 65% RH, mold forms and grows. In particular, photographic images use gelasene, which is rich in culture, and are suitable for mold growth.

For this reason, in the living environment of ordinary Japanese households, even wedding photos that are supposed to be kept with care often have mold that can be seen with the naked eye after 10 years.

Physical deterioration of the support and image layer, such as adhesion between screens or between screens and the back side, cracks on the screen, peeling of the crank image layer, shrinkage, embrittlement, and curling of the support, can be caused by high humidity, low humidity, and high temperature.
This is thought to be caused by repeated fluctuations in temperature and humidity, such as low temperatures.

This physical deterioration is fatal, and once it occurs, it usually ends the life of the image.

On the other hand, chemical deterioration is a type of deterioration that progresses over time through discoloration, fading, staining (coloring of the entire screen), etc., and eventually reaches the end of its life.

Chemical deterioration mainly involves redox and hydrolysis reactions, so the lower the temperature and humidity, the better to prevent it. It is also essential to isolate it from sources of oxidants, sulfur dioxide gas, ozone, chlorine gas, etc.

By the way, an attempt was made to preserve photographic images for a long time during the Osaka World Expo by treating microfilm images with gold compounds (goldenrichment) to make them more solid, storing them in capsules with an argon gas atmosphere, and storing them underground.

Furthermore, since 1986, the National Museum of Modern Art in Japan has built a new storage room with a constant temperature of 2℃ and humidity of 40%RH.
We are working hard to preserve photographic images.

At the J.F. Kennedy Memorial in the United States, the temperature is -180"C and the humidity is 20"C to preserve color photographic images.
The %RH repository was established in 1979.

However, the above method is very expensive and requires high maintenance costs, making it difficult to apply it widely.

In general households, a method is adopted in which prints are stored in a file and then wrapped in a packaging bag, or the prints are stored directly into a packaging bag.

Conventionally, such a packaging bag has a high-pressure branched low-density homopolyethylene resin (hereinafter referred to as LDPE resin) film layer as the innermost layer, and neutral paper laminated on the outside of the aluminum R1 intermediate layer as the intermediate layer. It was composed of laminates.

[Problem to be solved by the invention]

- In the conventional packaging bags mentioned above, the middle layer of aluminum foil corrodes, so photo prints can be stored for up to three years without deteriorating the image.
After 0 years or more, the image deteriorates even if stored in a cool place with low humidity.

The purpose of the present invention is to solve the above problems and provide a packaging bag that does not deteriorate the printed image for a long period of 10 years or more even under normal home conditions rather than special conditions. do.

[Means to solve the problem]

In order to achieve the above object, the present inventor conducted extensive research on the relationship between the above-mentioned image deterioration and packaging bags.

As a result, it was found that if the packaging bag contained a large amount of substances such as deli, fatty acids, etc., mold would grow.

The present invention was made based on the above research, and is a mold-resistant polyolefin resin film in which the innermost layer contains a total amount of mold-generating substances of 5% by weight or less and an ethylene copolymer resin of 5% by weight or more. It is composed of certain characteristics.

Mold-forming substances include starch, modified starch, and Polys.
Graft polymers with tylone-starch derivatives, plasticizers, saccharides, cellulose, proteins, amino acids, various fatty acids and fatty acid compounds, various lubricants, antistatic agents, natural rubber, vinegar vilatex, polyurethane resins, acrylic resins, soft PVC resins. , mold-producing adhesives, etc.

Representative examples of the above lubricants are shown below.

(1) Silicone lubricant; various grades of dimethylpolysiloxane, carboxyl-modified silicone oil (Shin-Etsu Silicone, Toshi Silicone, etc.) (2) Oleic acid amide lubricant; Armoslip CP (Lion, Akzo), Neutron (Nihon Seki) ratio), Neutron E-18 (Japan Manufacturing Co., Ltd.), Amide 0 (Nitto Chemical), Alflo E-10 (Nippon Oil & Fats), Diamid 0-200 (Nippon Kasei), Diamid G-200 (Nippon Kasei), etc. (3 ) Erucic acid amide lubricant; Alflo P-10 (NOF), Neutron S (Nihon Seikan) (4) Stearic acid amide lubricant; Alflo S-10 (NOF), Neutron 2 (Nippon Sanka) , Diamid 200 (Nippon Kasei), etc. (5) Bis fatty acid amide lubricant; Bisamide (Nippon Kasei), Diamid 200 Bis (Nippon Kasei), Armowax EBS (Lion, Akzo), etc. (6) Alkylamine lubricant; Electrostripper TS-2 (Kao Soap), etc. (7) Hydrocarbon-based lubricants; liquid paraffin, natural paraffin, microwax, synthetic paraffin, polyethylene, wax, polyethylene wax, chlorinated hydrocarbons, fluorocarbon, etc. (8) Fatty acid-based lubricants; (9) Ester-based lubricants Higher fatty acids (preferably 01□ or higher), oxyfatty acids, etc.; 00 alcohols such as lower alcohols of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, etc. Lubricant: Polyhydric alcohol, polyglycol, polyglycerol, etc. 01) Metal soap: Higher fatty acids such as lauric acid, stearic acid, ricinoleic acid, naphthenic acid, oleic acid, and Li, Mg%Ca, Sr, Ba, Zn, Cd5A
Compounds with metals such as f, Sn, and Pb will be explained in more detail below.

[Typical monoene unsaturated fatty acids]

cis-4-decenoic acid (obtusic acid), 9-decenoic acid (caproleic acid), 10-undecenoic acid (undecenoic acid), cis-4-dodecenic acid (lindelic acid), cis
-4-tetradecenoic acid (tuzic acid), cis-5-tetradecenoic acid (fisetheric acid), cis-9-tetradecenoic acid (myristoleic acid), cis-6-hexadenoic acid, cis-9-hexadenoic acid (palmitoleic acid) acid)
, cts-6-octadecenoic acid (petroselic acid), c
is-9-octadecenoic acid (oleic acid), trans
-9-octadecenoic acid (elaidic acid), Cl311-
Octadecenoic acid (asklepic acid), transll-
Octadecenoic acid (Bakusenjo), cis-9=eicosenoic acid (gadoleic acid), cis-11-tocosenoic acid (cetoleic acid), cis-13-tocosenoic acid (erucic acid)
, trans-13~tocosenoic acid (brassidic acid), c
is-15-tetradecenoic acid (ceracoleic acid), ci
s-i'7-hexadecenoic acid (xo, non-#), ci
s 23-triacontinic acid (rumecic acid) and the like.

(Light-chain saturated fatty acids) Butanoic acid (butyric acid), hexanoic acid (caproic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid (undecanoic acid),
Dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (valmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid),
Tocosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotic acid), octacosanoic acid (montanic acid), triacontanic acid (tarylic acid), etc.

[Special fatty acids]

Branched fatty acid 3-methylbutanoic acid (isovaleric acid), (+)-2
-Methylbutanoic acid (α-methylbutyric acid, isoacid, antiisoacid), D(-)-1,0-methyloctadecanoic acid (label clostearic acid), etc.

Fatty acids with triple bonds 6-octadecine M (tarylic acid), 9-octadecinoic acid (stearolic acid), cis-9-octadecene-
12-ynoic acid (talebenic acid), trans-11-
Octadecen-9-ynoic acid, etc.

Alicyclic fatty acid (stearic acid), ζ>CH,). C00H (human tucarpic acid), ζ%CH, tCOOCH=C
H(CHz)4cOOH (gol phosphoric acid), etc.

[Oxygen-containing fatty acids]

12-hydroxydecanoic acid (sabienoic acid), 2-hydroxytetradecanoic acid, 3,11-dihydroxytetradecanoic acid (ibrolic acid), 2-hydroxyhexadecanoic acid, (+)-11-hydroxyhexadecanoic acid (yarapinoleic acid), 16- Hydroxyhexadecanoic acid (univeric acid), 16-hydroxy-7-hexadecenoic acid (amprettolic acid), 9,10°16-)! J Hydroxyhexadecanoic acid (aluritic acid), 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9.10-dihydroxydioctadecanoic acid, (+)-12-hydroxy-9
-Octadecenoic acid (ricinoleic acid), 18-hydroxy-9,11,13-octadecatrienoic acid (camrolenic acid), 4-keto-9,1113-octadecatrienoic acid (ricanic acid), 22-hydroxytocosanoic acid (ferronic acid), 2-hydroxytetracosanoic acid (cerebronic acid)
etc.

[Typical polyene unsaturated fatty acids]

Diene unsaturated acid 2,4-hexadienoic acid (sorbic acid), trans
-2, cis-4-decadienoic acid, cis-9, ci
s 12-octadecadienoic acid (linoleic acid), t
trans-10, trans-12-octadecadienoic acid, etc.

triene unsaturated acid 6,10.14-hexadecatrienoic acid (hiragoic acid),
cis-9+trans-11,trans-13-octadecatrienoic acid (α-eleostearic acid), tr
ans-9, trans-11, trans-13-
Octadecatrienoic acid (β-eleostearic acid),
cis-9, trans-11+cis 13-octadecatrienoic acid (bunicic acid), cis-9+ci
s-12, cis-15-octadecatrienoic acid (lylunic acid), cis-6, cis~9. cis-12-octadecatrienoic acid (T-lylunic acid), 8,11.14
- eicosatrienoic acid, 7.10.13 ~ docosatrienoic acid, etc.

Tetraene unsaturated acids 4.8. ICl3-hexadecatetraenoic acid, 4,8.
12゜15-octadecatetraenoic acid (moloctic acid),
6゜9.12.15-octadecatetraenoic acid (stearidonic acid), 5,8. ICl3-eicosatetraenoic acid (arachidonic acid), 8,12,16.19-docosatetraenoic acid, etc.

Pentaene unsaturated acid 4, 8.12.15.18-eicosapentaenoic acid, 4
, 8,12°15,19-docosabencitric acid (Sardine M), etc.

Hexaene unsaturated acids 4.8.12.15.18.21-tetrachohexaenoic acid, cinnic acid), etc.

[Metal soap]

Lithium, copper, beryllium (mono), beryllium (di)
, magnesium, calcium, strontium, barium, zinc, cadmium, aluminum (mono), aluminum (tri), cerium, titanium, zirconium, lead, lead (dibasic), chromium, manganese, cobalt, nickel, etc.

[Fatty acid amide] Hydrogenated beef fatty acid amide, oleic acid amide, coconut fatty acid amide, N,N'-ethylenebisstearic acid amide, N
, N"-methylenebisstearamide, N,N-di(polyoxyethylene)alkanamide, coconut fatty acid monoethanolamide, lauric acid monoethanolamide, stearic acid monoethanolamide, coconut fatty acid jetanolamide (1 /1), palm fatty acid jetanolamide (1/2), lauric acid jetanolamide (1)
/1), stearic acid jetanolamide (1/1)
, oleic acid jetanolamide (1/1), stearic acid monomethylolamide, hexanoic acid amide, heptanoic acid amide, decanoic acid amide, lauric acid amide,
Myristic acid amide, valmitic acid amide, stearic acid amide, behenic acid amide, hexadecenic acid amide, eicosanoic acid amide, oleic acid amide, linoleic acid amide, linoleic acid amide, erucic acid amide, ricinoleic acid amide, etc.

The antistatic agent is shown below.

[Non-ionic]

Alkyl-polyoxyethylene-ether, P-alkylphenyl polyoxyethylene-ether, N, N-
Di(polyoxyethylene)alkylamine, NN-di(
polyoxyethylene) alkanamides, fatty acid polyoxyethylene esters, fatty acid sorbitan esters, fatty acid sorbitan = polyoxyethylene ether, fatty acid glycerin esters, alkyl polyethylene imines, etc.

[Anion type]

Aliphatic amine salts, alkyl phosphate salts, alkyl phosphate polyoxyethylene salts, alkyl sulfate salts, alkyl sulfate polyoxyethylene salts, etc.

[Cationic]

Alkylamine salts, alkyl quaternary ammonium salts (tetraalkylammonium salts, N,N-di(polyoxyethylene) dialkylammonium salts, N-alkylankanamide ammonium salts) alkylimidacillin derivatives (1-hydroxyethyl-2 -Alkyl-2-imidapurine, 1-hydroxyethyl-1-alkyl-2-
alkyl-2-imidacillin), etc.

[Bisexual]

Alkylbetaine form (N-alkylhetaine, N, N-
di(polyoxyethylene)alkylbetaine), alkylimidacillin derivative (l-carboxymethyl-1-hydroxy-1-hydroxyethyl-2=alkyl-2-
Imidacillin, 1-sulfoethyl-2-alkyl-2-
imidacillin), N-alkyl-β-alanine form (N-
alkylaminopropionate, N,N-di(carboxyethyl)alkylamine salt, etc.

The mold-generating adhesives mentioned above include emulsion adhesives such as polyvinyl acetate resin, vinyl acetate-ethylene copolymer, vinyl acetate and acrylic ester copolymer, vinyl acetate and maleate ester copolymer, and acrylic copolymer. There are emulsions such as polymers and ethylene-acrylic acid copolymers.

Latex adhesives include rubber latex such as natural rubber, styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), and chloroprene rubber (CR).

Adhesives for dry lamination include isocyanate adhesives, urethane adhesives, polyester adhesives, etc. Others include paraffin wax, microcrystalline wax, ethylene-vinyl acetate copolymer resin, and ethylene-ethyl acrylate copolymer. There are Hommel laminate adhesives, pressure-sensitive adhesives, heat-sensitive adhesives, etc. that are blended with coalescent resins, etc.

The total amount of the above-mentioned mold-generating substances must be within 5% by weight, preferably within 3% by weight, particularly preferably within 1% by weight. >150 R when exceeding 5% by weight
Mold growth was observed using the 846 test method, and mold growth cannot be prevented for a long period of time.

By the way, the growth conditions for mold are shown below.

(1) Moisture: They cannot grow at all in the absence of water or in pure water that does not contain impurities; they grow only in the presence of an appropriate amount of moisture. However, the only moisture available to microorganisms is free water, and other moisture (crystalline water, bound water, etc.) that is relatively strongly bound to substances cannot be used.

(2) PH...2-8.5 The most suitable pH for growth is a neutral range of around 7.

(3) Oxygen: Most molds require oxygen.

(4) Carbon dioxide - Growth of most molds is inhibited.

(5) Salt content: In order for microorganisms to grow, small amounts of inorganic salts (minerals) such as potassium, magnesium, manganese, iron, calcium, and phosphorus are necessary. However, the presence of salts in high concentrations actually inhibits growth.

Nutrition: In addition to the inorganic salts mentioned in (5), an energy source, a carbon source to form cell walls, a nitrogen source to form the proteins that form cells, etc. are required. Carbon sources include mono-VA such as fructose and glucose, oligosaccharides such as sugar and maltose, and polysaccharides such as starch and cellulose. Nitrogen sources include inorganic ammonium salts such as ammonium sulfate, ammonium phosphate, ammonium chloride, and ammonium nitrate. Organic nitrogen sources include urea, amino acids, and peptides.

Temperature: An important physical environmental factor that affects the growth rate of microorganisms, the enzymatic composition of cells, chemical composition, nutritional requirements, etc. The temperature range in which microorganisms can grow is approximately 7°C to 80°C. Generally, the optimum temperature for growth is 25°C to 45″C.

Therefore, in order to prevent mold from occurring, it is effective to set one or more of the above growth conditions outside the above range.
It is preferable to add a fungicide, sterilize, etc. at the same time.

Examples of fungicides are shown below. Some substances may have harmful effects on photographic materials, so it is necessary to consider the amount and location of addition (intermediate layer, outer layer, etc.).

■, Inorganic compounds (1) Copper and its oxides, salts, etc.

(2) Oxides, salts, etc. of zinc, chromium, mercury, cadmium, lead, etc.■, organic copper compounds (1) Copper naphtbenaLe-'' - trade name Cuprinol.

Nuodex Copper 8%, Nuocide
Copper 8%, Nopco.

Cordex, (Shinto Paint @) (2) Copper 8-quinolinolate
=Product name Mi1mer I Kunitate (3) Copper dtwethylglyoxim
e.

(4) Copper salts of fatty acids and other organic acids ■, non-copper metal organic compounds (1) Phenylmercuric acetate
---...Product name: Merselfe B, Hydrox
y Mildewproof 3-T.

(2) Phenylmercuric trietha
nolamine 1actate and oleate
.

(3) Phenylmercuric dinapht
hylmethane disulfonate...
...Product name Meltan (Shikinichi Yakuhin Kogyo ■) (4) P
yridylmercuric acetate.

(5) Zjnc ditsethyldithioca
rbataate...-Product name Zerlate, M
ethesan, Methazate, Methy
l Zinate.

■, Phenolic compound (1) Pen tach 1orophenop (P
CP) = =Product name Dowside 7+5anto
phene 20+ Mystolene, etc., Mitsui Chemicals, Hodogaya Chemicals, Chiyoda Chemicals, Dou Chemicals, Monsando, etc. (2) Trichloro, tetrachlor
o, o-phenyl-p-ni trophen
ol+ 2-chloro-o-phenyl-phe
nol et al.

(3) 2+ 2' -Methylened is-(
4-ch Iorophenol) = =Product name P
reventol GD, Cerol TG-1,D
, D, l'1. , G-4(4) Salicylani
ride--Product name 5hirla (Shinto Paint ■V, quaternary ammonium compound Trimethyloctadecylammoniu
Mpentachlorophenate・・・・・・
There are products containing aliphatic radicals with CI4 to 11 instead of 0ctadecyl 15.Product name: Hyamin
e 3258■, quinone compound (1) Tetrachloro-p-benzoqui
None.

(2) 2.3-Dichloro-1,4-napht
hoquinone.

(3) 2-Methy14,4-naphthoqui
none (Vitamine K,) -...Product name Kabinone (Kakoku Yakuhin) ■, Sulfur-containing organic compound (1) Tetrawethyl thiuram-di
sulphide.

(2) Dinetramethyl thiuram-a+
onosulfide.

(3) Rhodanine p-1sopropy1b
enzol-, Furfural-o-Chlorob
enzol derivative (4) 2+4 Dinitrophenylthioc
Yanate.

(5) 2-Mercaptobenzothiazol
e.

(6) 4- (2-Benzis+1dazolyl)
thiazole・・・-Product name Thiabendazole (
Merck & Co., USA) ■Others (1) Dyes and others = - Tannin, Azo dyes,
Altzarfn-2゜rndanthrenebri
lliant green h, Anil coppe
rblueB+ Aniline black etc. (2) Organic acid - Dehydracetic acid,
Propionic acid+5orbic ac
jd or its salts and benzoic acid compounds.

(3) Formaldehyde...Formalin and paraformaldehyde (4) Cresyl acetate (Cresati
n).

In addition, the following fungicides are commercially available: Vinyzene (Preventol A3, Morton International, USA) Briventol A4-5 (Preventol A4-5, Bayer, West Germany) 5) - "West German Bayer Briventol 0C3014 (Preventol 0C3014)" West German Bayer Briventol 0C3015 (Preventol 0C3015) - West German Bayer Sinthol AI? #100...Shinto Paint ■Neosyntol C...Shinto Paint ■Neosynthol AE...Shinto Paint ■Lobe Life...
...Shinto Paint■ o-Phenylphenol ・”=Sanko■, Doi
v Kabinone... Kansai Paint ■, Gakoku Yakuhin Kogyo ■ Particularly preferred fungicide compounds include 10゜10゛-oxybisphenoxyarsine, 2-methoxycarbonylaminobenzimidazole, 2-methoxy Mixture of carbonylaminobenzimidazole and N(fluorodichloromethylthio)phthalimide, N-dimethyl-N'-phenyl-N'(fluorodichloromethylthio)-sulfamide, N-(fluorodichloromethylthio)phthalimide, Thiabendazole, Pen tach Io
rophono I, 2-Melhyl-1゜4-na
phthoquino ne (vitamin Ks), τri
methylCetylammoniullpent
achlorophenolate, Sodium
dehydracetate, p-0xybenz
oic actd butylester, etc.

The amount added is 1-iooopp, preferably 5 to 200 pp.
m, particularly preferably 10 to 100 pp-.

(1) The main types of plastic barrier breakers will be explained in detail below.

Phenol ether derivative cio is the main antibacterial and fungicidal agent mixed into plastics or used for surface treatment.
, io'-oxybisphenoxyarsine, etc.), N-haloalkylthio compounds (dichlorofluanid, fluorofolpet, cabtan, etc.), imidazole derivatives (2-
(4-thiazolyl)benzimidazole, 2-methoxycarbonylaminobenzimidazole, etc.] and sulfone derivatives [2°3.5.6-titrachloro-4-(methylsulfonyl)pyridine, etc.] are known.

10,10''-oxybisphenoxyarsine is an organic arsenic compound, but it has relatively low toxicity, so it is incorporated into plastics and added to adhesives and water-based compositions to prevent the growth of mold and bacteria. .

N-haloalkylthio compounds such as dichlorofluanid are stable against heat treatment and have excellent antibacterial activity.

2-(4-thiazolyl)benzimidazole is also an extremely stable compound and is used for mold prevention at concentrations of about 0.005 to 1%.

(2) Other antibacterial and fungicidal agents for plastics As antibacterial and antifungal agents for plastics, anilide derivatives (3, 4°,
5-tribromusalicylanilide, etc.) pyrrole derivatives (
N-()dichloromethylthio)phthalimide, N-(fluorodichloromethylthio)phthalimide, N-trichloromethylmercapto-4-cyclohexene-1,2-
dicarboximide, N-C1,2,2-tetrachloroethylthiotetrahydrophthalimide, etc.], phenolics (pentabromophenol, chloro-0-phenylphenol, etc.), triazine [hexahydro-1,3,
5-) riethyl-S-triazine, etc.], quaternary ammonium salts [cetyldimethylethylammonium bromide, N
-(3-chlorallyl)heximinium chloride, etc.],
Urea-based (3-trifluoromethyl-4,4'-dichloro-N, N'-dichloro-N, N'-biphenylurea, etc.) and polyamide-based fungicides are known. In addition, organic copper-based agents (such as oxine copper), thiocarbamic acid derivatives, and the like are known as antibacterial and fungicidal agents for plastics. When 2-methoxycarbonylaminobenzimidazole and N-(fluorodichloromethylthio)phthalimide are used in combination, an antifungal effect with excellent synergistic effects, low toxicity, and good thermal stability is exhibited.

Sterilization can be divided into heat sterilization, which uses heat, and cold sterilization, which does not use heat. The former heat sterilization is pasteurization (
It is divided into pasteurization) and high temperature sterilization.
In terms of heating conditions, heat sterilization in the presence of moisture is called wet heat sterilization, and heat sterilization in the absence of almost any moisture is called dry heat sterilization. All microorganisms (including spores) are more easily killed by heat sterilization than by dry heat sterilization.

The thermal sterilization method involves heating at a temperature range of 60 to 120"C for several seconds to several tens of minutes. On the other hand, dry heat sterilization usually involves heating at a temperature of 140 to 160" C.
Heat in the temperature range of 0°C for 2-4 hours. As heating means, steam, high temperature water, microwaves, infrared rays, far infrared rays, electric heat, gas, hot air, etc. are used.

On the other hand, cold sterilization is classified into chemical sterilization, radiation sterilization, and other sterilization methods. For chemical sterilization, liquid sterilizers, gas sterilizers, solid sterilizers, and immobilized sterilizers are used.

The ethylene copolymer resin contained in the mold-resistant polyolefin resin layer includes ethylene/α-olefin copolymer resin,
Ethylene/acrylic acid copolymer resin, ethylene/vinyl acetate copolymer resin, ethylene/propylene copolymer resin, ethylene/ethyl acrylate copolymer resin, ethylene/methyl acrylate copolymer resin, ethylene modified resin , ionomer resins, etc., and these ethylene copolymer resins may be used alone or in combination of two or more types.

Among these, the low-pressure method has excellent heat-sealing properties, is significantly cheaper in manufacturing equipment construction costs and operating costs than the high-pressure branched low-density polyethylene resin produced by the conventional radical polymerization method, and has excellent physical strength. Ethylene/α-olefin copolymer resin (generally referred to as linear low-density polyethylene resin) and ethylene/ethyl acrylate copolymer resin are preferred.

Ethylene-vinyl acetate copolymer resin is also preferred, but if the vinyl acetate comonomer exceeds 25%, the acetic acid is strong and acetic acid is liberated, causing discoloration of the print, which is not preferred. Therefore, it is necessary to use a material containing 3 to 25% of vinyl acetate groups.

The above ethylene copolymer resin needs to be contained in the mold-proof polyolefin resin layer in an amount of 5% by weight or more, and if it is less than 5% by weight, the heat sealing strength over time, hot tack property, and contaminant sealing will deteriorate. The sealability cannot be ensured for a long period of time due to insufficient sealing properties.

Thermoplastic resins that can be added to the mold-resistant polyolefin resin layer include high-density polyethylene resin, polybutene-1 resin, styrene resin, polymethyl methacrylate resin, styrene acrylonitrile resin, and ABS.
Resin, polypropylene resin, crystalline propylene-α-olefin copolymer resin, modified polypropylene resin, polypropylene/water maleic acid graft copolymer resin, chlorinated polyolefin resin (mainly chlorinated polyethylene resin), polymethylpentene resin, chloride Examples include vinyl-propylene copolymer resin, polyisobutylene resin, 1,2-polybutadiene resin, EEA resin, and EVA resin.

Among these, it is preferable to contain 5 to 95% by weight of high-density polyethylene resin from the viewpoint of preventing blocking, improving moisture proofing properties, improving gas barrier properties, and improving slipperiness. If it is less than 5% by weight, the rigidity will be insufficient and the degree of crystallinity will be reduced, resulting in insufficient film formability, bag making properties, and anti-blocking properties, and if it exceeds 95% by weight, heat sealability, film formability, Problems arise in terms of tear strength, etc.

In the present invention, high density polyethylene resin refers to density (JTS
K-6760, ASTM D-1505) is 0.94
It means homopolyethylene resin and ethylene-α olefin copolymer resin of 0g10ff or more. Melt index (JIS K-6760, ASTM D-1)
238-E method) is 0.1 to 20 g/10 minutes, particularly preferably 0.3 to 5 g/10 minutes. the above,
By including high-density polyethylene resin in the innermost mold-proof polyolefin resin layer, blocking can be prevented without using a mold-generating lubricant or anti-blocking agent, or by using only a small amount. Further, since it has effects such as improving Young's modulus, improving lubricity, and improving light-shielding property, it is preferable to use it in the innermost layer.

The packaging bag of the present invention can have at least one light shielding layer. Examples of light-shielding substances used in the light-shielding 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, beryllium oxide, pumice, pumice balloon, alumina Fibers etc. B, hydroxides... aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, etc. C1 carbonates... calcium carbonate, magnesium carbonate,
Dolomite, dawsonite, etc., ()sulfite...calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, etc.E, silicate...talc, clay, mica, asbestos, glass fiber, glass balloon, glass peas, Calcium silicate, montmorillonite, bentonite, etc.F, carbon...graphite, carbon fiber, carbon hollow spheres, etc.G, others...iron powder, copper powder, lead powder, tin powder, stainless steel powder, burl pigment, aluminum powder, Molybdenum sulfide, boron fiber, silicon carbide fiber, brass fiber, potassium titanate, lead zirconate titanate, zinc borate, barium metaborate, calcium borate, sodium borate, aluminum paste, etc. Especially as light-absorbing light-shielding substances. Preferred carbon black will be explained in detail.

The amount added is preferably 0.05 to 5% by weight. If it is less than 0.05% by weight, light shielding properties, antistatic properties, antiblocking properties,
The oxidation prevention properties are insufficient and the cost of crosstalk increases (
When the wall thickness of the packaging material is 200p or less, 0.5% by weight or more is preferable). If it exceeds 5% by weight, the physical strength is reduced, moldability is deteriorated, dust generation increases, and the photographic material is stained black. Furthermore, the amount of moisture absorbed increases, which not only causes foaming during molding and deteriorates the appearance, but also increases the generation of free sulfur, which deteriorates the shelf life of the photograph.

It is preferable to knead carbon black so that the surface reflection density is 1.2 or more, preferably 1.4 or more in order to ensure light-shielding properties.

Carbon black can be used in various forms such as dry color liquid color, paste color, master patch pellets, compound color pellets, and granular color pellets, but the masterbatch method using master patch pellets is preferable in terms of cost, prevention of workplace pollution, etc. It is preferable. Japanese Patent Publication No. 40-26196 discloses a method for preparing a polymer-carbon black masterbatch by dispersing carbon black in a solution of a polymer dissolved in an organic solvent; A method is described in which a master bunch is prepared by dispersing in polyethylene resin.

The present applicant also published a resin composition for colored masterbatch in JP-A No. 6
This is proposed in the publication No. 3-186740.

Carbon black can be classified by raw material: gas furnace black, oil finesse black, channel black, anthracene black, acetylene black, ketchiene carbon black, conductive carbon black, thermal blank, lamp black, oil smoke, pine smoke,
There are animal blanks, vegetable blacks, etc.

In the present invention, furnace carbon black is preferable for the purpose of improving light shielding properties, cost, and physical properties. Carbon blacks that are expensive but have antistatic effects include acetylene carbon black, conductive carbon black, and ketchen carbon black, which is a modified by-product carbon black. Carbon black is preferred. If necessary, it is also preferable to mix two or more types according to the required characteristics.

In the present invention, carbon black produced by a furnace method is preferred, but carbon black produced by either a channel method or a thermal method may be used.

In addition, as actual products, for example, carbon black #20 (B), #30 (B), #3 manufactured by Mitsubishi Kasei.
3 (B), #40 (B), #44 (B), #45
(B), #50, #55, #100, #600, #2
200 (B), #2400 (B), MA8, MA
IL,? Examples include lA100.

As for overseas products, for example, Cabot's Black
Pearls 2.46.70.71.74.80.
81.607 etc. Regal 300.330.400
．． 660.991.5RF-5 etc.

Vulcan 3.6 etc. Sterling 10, S
Examples include O3M, S, FTFF, and MT-FF.

In addition, United R,B of Ashinyundo Chemical Co., Ltd.
B, 15.102.3001.3004.3006.3
007.3008.3009.3011.3012,X
Examples include, but are not limited to, C-3016, XC-3017, and 3020.

Flexible sheets can be laminated to improve bag-making suitability and various physical properties. Examples of flexible sheets are shown below.

Cellophane, OPP (stretched polypropylene film),
CPP (unstretched polypropylene film), PET (
polyester film), ONy (stretched nylon film), CNy (unstretched nylon film), vinylon film, ethylene vinyl alcohol copolymer film, K coat (abbreviation for vinylidene chloride coat) film (
K-coated cellophane, K:1-)OPP, to:I-)PE
T, ni: ]-) ONy, ni-coated vinylon (coated on both sides)), paper (imitation paper, high-quality paper, neutral paper, kraft paper, pure white roll paper, parchment paper, waterproof paper, glassine paper, etc.),
Aluminum foil, vapor deposited film (PET, ONy, OFF, C
PP et al.). When using paper, care must be taken to reduce the amount of mold-generating substances and decomposed substances used, and to add or coat a fungicide.

A thermoplastic resin extrusion adhesive can be used to laminate flexible sheets and the like. Examples of this thermoplastic resin extrusion adhesive are shown below.

Polyolefin thermoplastic resin hot melt adhesives such as various polyethylene resins and various polypropylene resins, ethylene and
Ethylene copolymer resins such as propylene copolymer resins, ethylene/vinyl acetate copolymer resins, ethylene/ethyl acrylate copolymer resins, ethylene/acrylic acid copolymer resins, ionomer resins, ethylene/methacrylic acid copolymers Extrusion adhesion of thermoplastic resins such as resins and ethylene/methyl methacrylate copolymer resins.

More specifically, polyolefin resin adhesives for extrusion lamination include various polyethylene resins, polypropylene resins, and ethylene copolymers (EVA, EE
A, etc.) In addition to resins, L-LDPE resins, which are made by copolymerizing ethylene with a portion of other heptamers (α-otophine), and ionomer resins such as DuPont's Surlyn and Mitsui Polychemical's Himilan. (ionic copolymer resin), Mitsui Petrochemical's Atmer, and Mitsubishi Yuka's MOD
IC and Dow Chemical's Primacol (thermoplastic resin,
Preferred examples include adhesive polymers (L7), which are graft-modified polyolefin resins and unsaturated carboxylic acids.

The thickness of the adhesive layer formed by the extrusion lamination method using a thermoplastic resin is usually 6p to 50-1, preferably Ion to 20n, but it may vary depending on the thickness, adhesive strength, lamination speed, total thickness of the laminate, etc. Since it is determined that
This value is not particularly limited.

Various antioxidants can be added to the various resins used in the present invention as necessary.

As antioxidants, phenolic ones include 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-5-t-butylphenol), 4.4'-thiobis(3-methyl6-t-butylphenol), 4 .4'-butylidene bis(3-methyl-6-t-butylphenol), stearyl-β(3,5-di-4-butyl-4-hydroxyphenyl)propionate, 1. L3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, L3,5-)listyl-2,4,6-)lis(3
, 5-di-t-butyl-4-hydroxybenzyl) Hensen, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, tetrakis(methylene-3(3',5°-di-t -butyl-4'-hydroxyphenyl)propionate comethane and the like.

As sulfur-based ones, dilauryl-3,3'-thiodipropionate, cimilistyl-3,3'-thiodipropionate, laurylstearylthiodipropionate,
Examples include distearyl-3'-thiodipropionate and ditridecyl-3,3°-thiodipropionate. Phosphorus-based substances include trinonylphenylphosphite and triphenylphosphite.

Among these, phenolic antioxidants are particularly preferred.

In particular, 2,6-di-tert-butyl-ρ-cresol (BHT)
) and low-volatility high molecular weight cresol type antioxidants (trade name 1reganox 1010, lreganox 1
076, Topano ICA, l0nox 330
etc.), dilaurylthiodipropionate, distearylthiodipropionate, sialkisphosphate, etc. It is effective to use one or more, especially two or more of them in combination.

The total amount added is preferably 0.001 to 1.0% by weight, whether used alone or in combination of two or more.

If the amount added is less than 0.001% by weight, there is almost no effect of the addition. On the other hand, if the amount added exceeds 1.0%, the photographic film that utilizes oxidation and reduction effects may be adversely affected and abnormalities may occur in performance. For this reason, it is preferable to add the antioxidant in the minimum amount that will not cause color failure or blistering.

Preferred antioxidants as commercially available products include various Irganox products from Ciba Geigy and Sumil-izer from Sumitomo Chemical.
BHR, Sumilizer BP-76, 5ul
ilizer WX-R.

Examples include Sumflizer 0P-101.

In addition, when used in combination with carbon black etc., the oxidation prevention effect is synergistically exerted.

The outermost layer of the packaging bag preferably contains 5% by weight or less of a degradable synthetic polymer. This degradable synthetic polymer has
There are microbially degradable synthetic polymers and photodegradable synthetic polymers. This will be explained in detail below.

■ Microbially degradable synthetic polymers (a) Synthetic polymers containing starch, etc.) Synthetic polymers containing modified starch (C) Synthetic polymers containing skin powder and micronized cellulose (6)
Synthetic polymers produced by microorganisms (polyhydroxypolyester, etc.) (e) Synthetic polymers containing polycaprolactone Polymers themselves are microbially degradable) Typical examples of microbially degradable synthetic polymers produced by fermentation such as PVA, PEG, polyurethane, nylon, polyester, etc. is described below.

(1) Polyesters (Microbial Polyesters)
esters) Poly(3-hydroxybuty
rate) ; Abbreviation P (3HB) (2) Copolyesters (Structure) CH.

H-(OCHCH2CO)n-OH (a) Po1y(3-hydroxybutyra
te-CO-3-hydrooxyValerate)
; Abbreviation P (3HB-GO-3HV) (Structure)? H・ C・H・ H-(OCHCHzCO) ト(OCHCHzCO)
n-0H (38B) (3HV) (0)
Po1y(3-hydroxybutyrate-
CO-4-hydroxybutyrate) ; Abbreviation P (3HB (Structure) L H-(OCHGHzCO) I!1- (OCH2CH
2CH2CO) n-0H(3HB) (
4HB) (c) Copoly(3-hydroxyalkan
oate) ; Abbreviation 4HB) P (3HA), etc. (3) Polysancalides (a) Bacterial cellulose (+7) Dextran (c) Pullulan (d) Curdlan (xanthan gum) Gellan gum (4) Polyamino acids (a) ε-polylysine (u) r-polyglutamic acid (c) PolyT-methyl-L-glutamate, etc. Accelerator of microbial decomposition Starch (also called starch. Also includes modified starch. Types include cornstarch, potato, starch, and rice. Typical product names and manufacturers that are commercially available as masterbatches made by blending starch, etc.) with synthetic polymers at high concentrations are listed below.

(a) ``EC05TAR'' Canada st, Lawrence
ce 5tarch Co.

It is a masterbatch for microbially degradable synthetic polymers, and its composition is thought to be as follows.

Cornstarch 40-t% (starch surface treated with silane coupling agent) Polyethylene resin 60wt% Soybean oil Small amount (unsaturated fatty acids) (Ill) “EC0STARplus Canada St, Laeyrence 5tarch C
o.

An organic metal with UV activity is added to the above (() EC05TAR, giving it photodegradability and microbial degradability.

(c) “Polyclean” Archer Da, USA
niels midland co.

This is a masterbatch for microbially degradable synthetic polymers, and the composition is almost the same as "EC05TAR" in (a) above.

(D) “Poly-Grade II” U.S. Amp
acet Co.

Almost the same composition as (a) above.

(ne) 'Po1y-Grade m'USA Aspac
et Co.

Almost the same composition as (a) above.

■ Photodegradable synthetic polymer (1) A synthetic polymer containing starch whose surface has been treated with a silane coupling agent, an unsaturated fatty acid, and an organic metal (2) A combination of a vinyl ketone compound and polyethylene resin, polypropylene resin, and polystyrene resin. Copolymer resin.

(3) Ethylene/Co/VAC terpolymer resin.

Oxidative decomposition proceeds even in the absence of light.

(4) Polymer chain scission due to radical generation in cerium stearate additives (for PE and PP) or cerium caprylate additives (for PS).

(5) A combination of a metal organic compound such as iron stearate and an additive such as 4-chlorobenzophenone (a combination of a photolysis accelerator and an oxidation accelerator).

(6) Adding iron compounds and nickel or cobalt compounds to polyethylene resin, etc.

(7) A combination of antioxidants and transition metals (iron, nickel, etc.) is added to synthetic polymers.

(8) Copolymer resin of ethylene and carbon monoxide (carbonyl groups are dispersed and introduced into the linear chain) (DuPont, UCC, and Dow Chemical in the United States are currently commercializing it as an ECO copolymer).

Manufactured by Union Carbide and Oow Chemica in the United States.

In the main chain of polyethylene resin - Introducing carbon oxide. Due to ultraviolet rays The main chain is cleaved (carboxylated) The second carbon counting from the nyl group The chain between the element and the third carbon is broken. reaction) decomposes.

(9) A method of mixing a photodegrading agent with a synthetic polymer.

Substances that perform hydrogen abstraction reactions from synthetic polymers by photoexcitation, such as ketones such as benzophenone and quinones such as anthraquinone (also called photodecomposers or photosensitizers)
mixed with synthetic polymer.

Even with just a packaging bag and under normal household storage conditions,
As a packaging material for packaging bags that will not deteriorate the printed image for a long period of 10 years or more, the innermost layer has a total amount of mold-generating substances of 5 IC% or less and an ethylene copolymer resin of 5 IC.
It is not only a mold-proof polyolefin resin layer containing more than % by weight (it is essential that it has at least one light-shielding layer).
0208) is Log/Bo・24 hours (40℃・90%
RH) or less, preferably 5 g/bo・24 hours, particularly preferably Ig#+(・24 hours or less, oxygen permeability (AST)
MD 3985 US Modern Control 1
(measured with a company-made 0xtran measuring device) is 100cc/rrf
・Sealing the print in a light-shielding, moisture-proof, and oxygen-barrier packaging bag using a packaging material that has a pressure of less than 50 cc/rrr/hour/atmosphere, preferably 25 cc/rd/hour/atmospheric pressure or less, and particularly preferably 25 cc/rd/hour/atmosphere. After that, it is preferable to use a method in which the product is stored at a temperature of 23° C. or lower, preferably 20° C. or lower, particularly preferably 15° C. or lower, where mold growth is difficult. For example, refrigerators, low-temperature warehouses, etc. Furthermore, the storage humidity is 70%RH or less, preferably 60%RH or less.
%RH or less, particularly preferably 50%RH or less, is preferably used in combination.

For example, it is suitable for low-temperature storage using a desiccant agent and the packaging bag for long-term storage of prints of the present invention, which has a mold-resistant polyolefin resin layer with low moisture permeability and light-shielding and sealing properties with low oxygen permeability. is preferred. Typical specific examples of packaging materials are listed below, but the present invention is not limited to these, and the present invention is not restricted to these typical examples in any way unless it exceeds the gist thereof.

[Packaging material for light-shielding packaging bags of the present invention] Typical specific example]

A packaging material that is light-shielding and has a moisture permeability of 10 g/bo/24 hours or less, and an oxygen permeability of 100 cc/rrr/hour/atmospheric pressure or less.

(1) Simultaneous two-layer coextrusion inflation/shading film! 20. ! Fil (Titanium oxide 6wt%λ) IDPE
Layer 6o# x carbon black 3wt%, silica 0.2w
t%, lubricant Q, 1wt% λL-LDPE layer 60n) (2) K: 7-tocellophane 20n/adhesive layer LDPE 1
5tna/AI2 foil 7 n/L-LDPH30wt%λ
LDPI4 cloth layer 30° (3) Af vapor deposition (400 people) ON
y film 15n/adhesive layer LDPE 15n/simultaneous two-layer coextrusion inflation light-shielding film 55n (
HDPE layer 25n carbon black 3wt%A L-
LDPE layer 30n) (43K: ff-to OP P 7
i JLtmu 20n/adhesive layer modified PO20wt%λLD
PH15n/force-bon black 3wt%, HDPE20
wt%λL-LDPE light shielding film 701! m(5) Synthetic paper 50n/Adhesive layer LDPE 15u/A, l! Foil 9aw/EEA30wt%λL D P E coating layer 35
n(6) Glassine paper 40-/adhesive layer LDPH15n/A
j! Foil 91/Adhesive layer LDPE 15uts/Barium sulfate Fvt%, L-LDPE light shielding film 60 (7) Titanium oxide 5wt%λ Biaxially stretched PET film 1
2n/adhesive layer LDPE 15n/Al foil 74/adhesive layer LDPII! 15n/Titanium oxide 5wt%, lubricant 0,
2 wt% λL-LDPE light shielding film 50n (8) Titanium oxide 5 wt% λ biaxially stretched PET film 1
2n/adhesive layer LDPE 15n/Af vapor deposition (400 people)
ONy15n/adhesive layer LDPE 15n/force-bon 3w
t%, lubricant 0.1wt%, HDPH5wt%λL-LD
PE light shielding film 6on (9) Silica 0.2wt%λ Biaxially stretched PET film 12n/Adhesive layer LDPH15n/
AI! Vapor deposition (400 people) OEVOH20tna/adhesive layer LDPH154/simultaneous two-layer coextrusion inflation light shielding film 60n (carbon 3wt% λ HDPE layer 30., fungicide 0, 05w t%λ x lubricant 0.1w
t%, antifog agent 0.2wt%λ, L-LDPE layer 30n)
0ωAffi vapor deposition (400 people) ONy film 15-/
Carbohydrate 3wt%, L-LDPE 20wt%λLDP
E coating layer 60n (IDK coat ONy film 151/
Carbon 3t%, L-LDPH20wt%λLDPE
Coating layer 60nOEK+-T PET film 15ym
/carbohydrate 3wt%, L-LDPE 20wt%λLD
PE coating layer 60-QEI K D-to EVOH film 15fm/carbon 3+mt%, L-LDPH 20wt
%λLDPE coating layer 60n (14) All! Vapor deposition (40
0 people) LDPE film 30n/carbon 3wt%,
L-LDPE 20wt%λLDPE coating layer 60° (1
51Al vapor deposition (400 people) CPP film 25-/carbon 3eit%, L-LDPH 20wt%λLDPE
Coating layer 60nOω 0.05wt%, HDPE 20
wt%λ, titanium oxide 6wt%λL-LDPE film 50n/adhesive layer LDPE 15-/A I foil 1trm/
Vapor deposited layer LDPE 15n/Lubricant 0, 05wt%, Silica 0.05wt%, Carbon black 3ht%λL-
LDPE film 50n O'7) Titanium oxide 611t%λ diagonal uniaxial stretching)! DP
E film 45 lines/Adhesive layer LDPH15m/Carbon 4
5wt%, L-LDPE20wt%λ diagonal uniaxial stretching HD
OE film 50. N-side synthetic paper 50n/adhesive layer LDPH
15trm/Ai vapor deposition (400 people) ONy film 15
n/Adhesive layer LDPE 15-/Lubricant 0.05wt%, H
DPH15 wisdom t%λ L-LDPE film 50-(1
9) PET nonwoven fabric 70 μs/adhesive layer LDPE
15 Immediate/An vapor deposition (400 people) ONy film 15Jr
m/adhesive layer LDPE 15 instant/lubricant 0.05wt%, H
DPE 15wt%λL-LDPE film 5〇-■ Biaxially stretched PET film 12μ/adhesive layer LDPE 15n
/Af foil 7m/adhesive layer/LDPH151/ E E A
20wt% λCPP film 50n an biaxially stretched PET film 12n/adhesive layer modified PO2
0n/Iron foil 25n/Adhesive layer modified PO20trm/Lubricant 0
．． 5wt%,) IDPE 10%4t%λL-LDPE
Film 501IM (explanation of abbreviations) K coat: Vinylidene chloride compound coating L DPE: High pressure branched low density homopolyethylene L -LDPE: Low pressure direct branched low density homopolyethylene AI! , Nialuminum foil HD P Es High density polyethylene (including homo and copolymer) ONy: Biaxially oriented nylon OP p: Biaxially oriented polypropylene EEA: Ethylene ethyl acrylate copolymer PET: Polyethylene terephthalate 0BVOH: Biaxially oriented ethylene/acetic acid Saponified vinyl copolymer EV OH: Saponified ethylene/vinyl acetate copolymer (eval, manufactured by KK Kurera, etc.) Abbreviation for modified polyolefin (also referred to as adhesive polyolefin) The packaging bag for long-term storage of prints of the present invention has a haze of 8.
In the case of translucent or transparent packaging bags that use 0% or less packaging material, even if the seal is secure, the print will deteriorate due to light, so use in combination with a light-shielding sheet, light-shielding bag, or light-shielding container that has light-shielding properties. Even if this is the storage condition for ordinary households, it is essential to preserve printed images for a long period of 10 years or more.

The purpose of sealing and storing prints in translucent or transparent packaging bags with a haze of 80% or less is to enable them to be taken out and admired during long-term storage for a couple's lifetime or for two or more generations.In this sense, the present invention This also includes a sealing method in which a translucent or transparent print with a haze of 80% or less can be viewed from outside the packaging material by deaerating the packaging material and adhering or laminating it to the print surface.

Even in this case, the total amount of mold-forming substances in the innermost layer is 5.
It is essential that the mold-resistant polyolefin resin layer contains 5% by weight or more of ethylene copolymer resin.

In addition, one or more antifogging agents or Preferably, the moisture-absorbing polymer is included in the innermost layer.

For example, if you take the prints out of the refrigerator or low-temperature storage in the summer and try to observe them, problems may occur such as countless small water droplets adhering to the packaging bag, making it difficult to see the prints inside the packaging bag, or water droplets adhering to the prints. do. In the present invention, in order to solve the above-mentioned problems, water droplets on the surface of the innermost layer are formed by kneading a water-absorbing substance or an antifogging agent into at least the innermost layer, bleeding out from the intermediate layer to the innermost layer, or coating it on the surface. or by increasing the surface tension of the innermost layer, increasing its hydrophilicity and breaking the shape of water droplets so that the entire surface is evenly wetted, improving light transmission and allowing the print inside the packaging bag to be better viewed. It is preferable to However, since this antifogging agent bleeds out to the surface of the innermost layer, blocking occurs and heat sealability deteriorates in this case. For this improvement, it is preferable that the innermost layer contains an anti-bronching agent and a high-density polyethylene resin.

In addition, it is preferable that one or more layers of the packaging material used in the translucent or transparent packaging bag of the present invention contain various ultraviolet absorbers during long-term storage under conditions where ultraviolet rays are present, such as under sunlight or fluorescent lighting. This is preferable in terms of preventing fading and deterioration of prints when viewing them.

Representative examples of this ultraviolet absorber are shown below.

Many substances are known as ultraviolet absorbers. For example, 2-(2°-hydroxy-5″-tert −
butylphenyl)benzotriazole, 2-(2'-hydroxy-3"-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-
Hydroxy-5”-dodecylphenyl)benzotriazole, 2-(2”-hydroxy-3’,5’-di-te)
r t-butylphenyl)benzotriazole, 2-(
2''-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 5-methyl-2-(2'-hydroxy-5'-isooctylphenyl)benzotriazole, 5-octyl -2-(2
'-Hydroxy-5'-isooctylphenyl)benzotriazole, 5-chloro-2-(2'-hydroxy-
3''-n-amyl-5'-phenyl)benzotriazole, 5-phenyl-2-(2'-hydroxy-5'-di-t-amylphenyl)benzotriazole, 2-(2
゛-Hydroxy-5''-cyclohexylphenyl)-5
-Chlorobenzotriazole, 2,4.6- ) Lis(
o-(2H-benzotriazol-2-yl)-4-methylphenyl)-s-)riazine, P-(2H-benzotriazol-2-yl)phenylbenzoate, 3-methylphenyl-4-(2-benzotriazole) ) benzoate, bis(5-(2H-benzotriazole-2-
yl)-4-methylphenyl two-carboxylate and the like are used, but are not limited thereto.

In the case of a packaging bag for long-term storage of prints using a packaging material with a haze of 80% or less, the bags are subject to chemical and photochemical deterioration due to light emission when left indoors in this state.

In order to prevent chemical and photochemical deterioration caused by this light, it is preferable to use it in combination with a light-shielding sheet (including a light-shielding film), a light-shielding bag, or a light-shielding container. This is an essential condition if it is not stored.

Even when these light shielding means are used in combination with the translucent or transparent print packaging bag for long-term storage of the present invention, the oxygen permeability and moisture permeability as a result of the combination use are the same as the light shielding properties,
It is preferable to set the same value as when using a moisture-proof and oxygen-barrier packaging bag.

Especially when the average number of viewings is likely to be two or more times a year, the moisture permeability is 10g/rrf・24 hours (40℃・
90%RH) or less, oxygen permeability is 100cc/rrf・
It is preferable to store the product at a temperature of 23°C or less after sealing it in a moisture-proof and oxygen-barrier packaging bag using a packaging material that can withstand hours and atmospheric pressure.

In addition to the above-mentioned packaging bag of the present invention, the light-shielding bag may be moisture-proof,
A light-shielding bag having light-shielding properties with poor oxygen barrier properties can be used. As the light-shielding container, any light-shielding container such as a cardboard box, chest of drawers, paulownia box, light-shielding plastic container, or metal container can be used. Particularly preferred are light-shielding plastic containers and metal containers whose fitting portions are sealed with a tape or the like that has moisture-proofing properties, oxygen barrier properties, light-shielding properties, print protection properties, and waterproof properties.

Moisture permeability is 10g/rrI・24 hours or less, oxygen permeability is 100cc/rrf・hour・atmospheric pressure or less, haze is 80%
The following innermost layer is preferably applied to the printed long-term packaging bag of the present invention, which is a mold-resistant polyolefin resin layer. Typical specific examples of packaging materials are listed below, but the present invention is not limited thereto, and the present invention is not restricted to these representative examples in any way unless it exceeds the gist thereof.

[Representative specific examples of packaging materials for packaging bags with a haze of 80% or less according to the present invention] (1) Single layer blown film (anti-fog 1fFIo
, 1wt%, lubricant 0.05t%, antioxidant 0.1i
vt%, HDPE 5gt%λL-LDPE film 1
00am) 100a coated cellophane 26n/adhesive layer LDPE 15
fl/L-LDPE 20wt%λLDPE film 8
0n(3) K coated OPP film 20IIM/Adhesive layer LDPH15, IQII/L-LDPE 20wt%
λLDPE film 80. n(4) K coat 0Ny15
n/adhesive layer LDPE 15Hzm/antifog agent 0.05-t
%, lubricant 0.05wt%, LDPH10wt%λL-L
DPE film 10n (5) Biaxially stretched PET film 12-/Adhesive layer LDPE
15p/ ON y 1.5. n/adhesive layer LDPE
15m/antifogging agent 0.1wt%, lubricant 0.05wt%,
LDPE 5wt%,) IDPE 5wt%λL-LD
PE film (6) Biaxially stretched PET film 12n/adhesive layer LDPE
15.10EVOH20n/adhesive layer LDPH15n
/ Antifog agent 0.1wt%, lubricant 0.05-t%, LDPE
51%,) IDPE 50% λL-LDPB film (7) Simultaneous two-layer coextrusion blown film 12
0-(antifog agent 0.1wt%λHDPE layer 50-x lubricant 0
．． 05 yoke t%, antifogging agent 0.1wt%, silica 0.1wt
%λL-LDPE layer 70n) (8) Simultaneous three-layer coextrusion blown film 10
0n (0.1wt% lubricant λNy layer 20n x modified PO layer 1
5n x antifog agent 0.1wt%, lubricant 0.1wt%, antioxidant o, it%, ultraviolet inhibitor 0.05wt%,)
IDPE 10wt% λL-LDPE layer 65n) (9) Simultaneous four-layer coextrusion blown film 10
0n (0.1wt% lubricant λNy layer ts, X EVOH
Layer 20n modified PO layer 15Q x antifogging agent 0.1wt%, lubricant 0.05wt% λL-LDPE layer 50μ) (Explanation of abbreviations) Ny: Unstretched nylon The packaging bag of the present invention has a haze (JIS K 6714). 8
When forming the film to be transparent with a transparency of 0 or less, it is preferable to add an antifogging agent. Representative examples of antifogging agents are described below.

Sorbitan-based surfactants such as sorbitan monostearate, sorbitan monopalmitate, sorbitan monobenzoate, etc.

Glycerin surfactants such as glycerin monolaurate, diglycerin monopalmitate, glycerin monostearate, etc.

Polyethylene glycol surfactants such as polyethylene glycol monostearate and polyethylene glycol monopalmitate.

Alkylene oxide added to the above surfactant Alkylphenol/formalin condensate, benzylated phenol/formalin condensate, N,N-bis(2-hydroxyethyl) fatty acid amide, N,N-bis(2-hydroxyethyl) Stearylamine, polyoxyethylene sorbitan fatty acid partial ester, alkylbenzene sulfonate, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, etc. moreover,
JIS Z 02 packaging bags that have light-blocking properties and are used to store prints for long periods of time even in ordinary households
The moisture permeability (=water vapor permeability) by the cup method of 08 is 10
g/rrf・24 hours or less, preferably 5g/rrf・24
hours or less, particularly preferably Ig/Bo・24 hours or less, A
STM 03985 (U.S. Modern Contr.
Oxygen permeability (20°C, 0% RH) measured with O1 Oxtran measuring device) is 100 cc/hr/atm or less, preferably 50 cc/rrf/hr/atm,
Particularly preferably, it is 25 cc/rr (・hour・atmospheric pressure) or less.

Using the above-mentioned packaging bag, the temperature is 23°C or lower, preferably 20°C or lower, particularly preferably 10°C or lower, and the humidity is preferably 7.
It is preferable to store it in a low-temperature storage at 0% RH or less, particularly preferably 50% RH or less, or in a low-temperature, low-humidity storage.

Prints to be stored in the packaging bag of the present invention include photographic prints such as color prints, black and white prints, instant prints, and thermal prints; photographic prints such as microfilm, computer typesetting, melay film, and printed photosensitive materials; color prints; This includes all general prints that require long-term storage, such as black and white printed books, reproductions, electrostatic copies such as color copies and black and white copies, paintings, and movie films.

In addition, the packaging bag of the present invention can be suitably used for packaging precision measuring instruments, meters, and the like.

[Effect]

The packaging bag for long-term storage of prints of the present invention prevents mold from forming in the innermost layer because the total amount of mold-generating substances is 5% by weight or less, and the ethylene copolymer resin is 5% by weight or more. Good heat sealability. moreover,
Furthermore, the anti-fog agent prevents the print inside the packaging bag, which has a haze of 80% or less, from becoming difficult to see even if the product is taken out and viewed during long-term storage at low temperatures.

[Example] Examples of the long-term storage packaging bag having print light-shielding properties of the present invention will be described based on FIGS. 1 to 8.

1 to 8 are partial cross-sectional views showing the layer structure of the packaging material used in the packaging bag for long-term storage of prints.

The packaging bag for long-term storage of prints shown in FIG. 1 is formed of a single layer of a mold-proof polyolefin resin layer 1a containing a light-shielding substance.

The packaging bag for long-term storage of prints shown in FIG. 2 is made of a two-layer coextruded blown film 3a consisting of a mold-proof polyolefin resin layer 1 and a thermoplastic resin layer 2a containing a light-shielding substance.
It is formed of.

The packaging bag for long-term storage of prints shown in FIG. 3 is formed of a two-layer coextruded blown film 3a consisting of a mold-proof polyolefin resin layer 1a containing a light-shielding substance and a thermoplastic resin layer 2a containing a light-shielding substance. .

The packaging bag for long-term storage of prints shown in Fig. 4 is made by directly laminating a mold-proof polyolefin resin layer 1, a thermoplastic resin layer 2a containing a light-blocking substance, and a thermoplastic resin layer 2 not containing a light-blocking substance. It is configured.

The packaging bag for long-term storage of prints shown in FIG. 5 is made of a blocking adhesive film 4a in which the thermoplastic resin layers 28 of the two-layer coextruded blown film 3a shown in FIG. 2 are bonded together by blocking.

The packaging bag for long-term storage of prints shown in FIG. 6 includes a mold-proof polyolefin resin layer 1, a metal-deposited flexible sheet 7 obtained by processing a metal-deposited film 6 on a flexible sheet 5,
They are laminated with a thermoplastic resin extrusion adhesive layer 8 interposed therebetween.

The packaging bag for long-term preservation of prints shown in FIG. It is formed by laminating flexible sheets 5 with an adhesive layer 8 in between.

The packaging bag for long-term storage of prints shown in FIG.
and paper 10 are sequentially laminated via a thermoplastic resin extrusion adhesive layer 8.8.

Examples of the packaging bag for long-term storage of prints having a haze of 80% or less according to the present invention will be described with reference to FIGS. 9 to 16.

9 to 14 are partial cross-sectional views showing the layer structure of the packaging material used in the packaging bag for long-term storage of prints.

The packaging bag for long-term storage of prints shown in FIG. 9 is formed of a single layer of a mold-proof polyolefin resin layer 1a that does not contain a light-shielding substance.

The packaging bag for long-term storage of prints shown in FIG. 10 is made of a two-layer coextruded blown film 3 consisting of a mold-proof polyolefin resin layer 1 and a thermoplastic resin layer 2.

The packaging bag for long-term storage of prints shown in FIG. 11 includes a mold-proof polyolefin resin layer 1, an intermediate layer 11, and a thermoplastic resin layer 2.
It is formed of a three-layer coextruded blown film 12 with

The packaging bag for long-term storage of prints shown in FIG. 12 is made of a blocking adhesive film 4 in which the thermoplastic resin layers 2 of the two-layer coextruded blown film 3 shown in FIG. 10 are bonded together by blocking.

The packaging bag for long-term storage of prints shown in FIG. 13 is formed by laminating a flexible sheet 5 on a mold-proof polyolefin resin layer with a thermoplastic resin extrusion adhesive layer 8 interposed therebetween.

The packaging bag for long-term storage of prints shown in FIG. 14 is formed by laminating a flexible sheet 5 on the two-layer coextruded blown film 3 shown in FIG. 10 with a thermoplastic resin extrusion adhesive layer interposed therebetween.

FIG. 15 and FIG. 16 are cross-sectional views showing a packaging state for ensuring light-shielding properties that are used in combination when a packaging bag for long-term storage of prints with a haze of 80% or less is used.

Figure 15 shows the print P sealed in a print long-term storage packaging bag TB with a haze of 80% or less that allows the print to be viewed from outside the packaging bag, and then placed inside a light-shielding container with a valve lid fitting type. It is a cross-sectional view of a state where the part is completely sealed with adhesive tape T.

FIG. 16 shows that Purin I-P is sealed and packaged in a long-term print storage packaging bag TB, which has a haze of 80% or less and allows the print to be viewed from the outside of the packaging bag, and has a light-shielding property. It is a cross-sectional view of a double bag sealed with a light-shielding bag BB, which preferably has moisture-proofing properties, oxygen barrier properties, and waterproof properties.

In this case, the main purpose of sealing the light-shielding bag is to block light, and various sealing methods include, for example, folding the entrance and then fastening with tape or adhesive, fastening with Velcro, and envelope method using pressure-sensitive glue. Various publicly announced methods can be used, including opening and sealing, completely sealing with heat sealing or impulse sealing, and using parts to seal the entrance.

Invention Product I Melt Index (hereinafter referred to as MI) (ASTM
Ethylene/4-methylpentene-1 copolymer resin with a density (ASTM D 1505) of 0.920 g/dT and a crystallinity of 43%. %, old 1.1 g/10 min, density 0.954 g/ad, crystallinity 90% high density homopolyethylene resin 10% by weight, n-octadecyl-3-
(4'-hydroxy-3',5'-di-t-butylphenol)propionate 0.05% by weight, silica 0.1
Thickness of the innermost layer free of mold-generating substances consisting of 5% by weight
0u mold-resistant polyolefin resin layer and Ml is O-4
g/10 min, density 0.964 g/cd, high density homopolyethylene resin 92% by weight with crystallinity 93%, old 9.4 g/10 min, density 0.923 g/cd
, an outermost layer of mold-forming material consisting of 5% by weight of a low-density homopolyethylene resin with a degree of crystallinity of 56%, an average particle size of 21y, a pH of 8.0, and 3% by weight of furnace carbon black with a volatile content of 0.8% by weight or less. After sealing the bottom of a 150n thick light-shielding two-layer coextruded blown film tube consisting of two layers, including a 100n thick thermoplastic resin layer and a 100n thick thermoplastic resin layer, the color print is inserted through the opening at the top, and the color print is inserted through the opening at the top. This is also a heat-sealed packaging bag for long-term storage of prints. The packaging material for the packaging bag corresponds to FIG.

This packaging bag not only does not show mold growth to the naked eye using the ISOR846 test method, but also has a temperature of 30°C and 90% RH.
Even after being left for 0 days, the heat seal strength decreased by less than 10%, and waterproofness was reliably ensured.

Water vapor permeability was 2.8 g/% for 24 hours.

Inventive product■ Old 2.0g/10min, density 0.920g/cn, crystallinity 48% ethylene-octene-1 copolymer resin 79.85% by weight, old 1.1g/10 minute, the density is 0.
954 g/cffl, 20% by weight of high-density homopolyethylene resin with 90% crystallinity, tetrakis[methylene-3-
A mold-proofing film with a thickness of 10 nm consisting of 0.05% by weight of (3,5-di-t-butyl-4-hydroxy-phenyl)propionate cometaf and 011% by weight of talc with an average particle size of 3. The old polyolefin resin film was 5.1g/10 minutes, and the density was 0.919g.
Aluminum vacuum evaporated biaxially stretched film with a thickness of 600 mm on a biaxially stretched polyester resin film with a thickness of 12s via a low density homopolyethylene resin extrusion adhesive layer (thickness 15n) of /cd This is a packaging bag for long-term storage of prints, using a packaging material laminated to an aluminum vacuum-deposited film of polyester resin film, and after inserting a color print through the opening of a flat bag that is sealed by heat-sealing on three sides, the opening is also sealed by heat-sealing. . The packaging material for the packaging bag corresponds to FIG. This packaging bag not only does not show mold growth to the naked eye using the ISOR846 test method, but also has a 30'C/90% IIIH rating.
Heat seal strength decreases by 10% even after being left for 30 days.
It had excellent waterproof, moisture-proof, and oxygen barrier properties. The water vapor permeability was less than Ig/rrr for 24 hours.

Inventive product■ Polyolefin resin layer with the same resin composition as the mold-resistant polyolefin resin layer with heat-sealability used in Inventive product ■ (however, thickness 50n)/Low thickness of 15n used in Inventive product ■ Density homopolyethylene resin extrusion adhesive layer/aluminum foil with thickness 7n/thickness 15 as above
A packaging bag for printed long-term storage using a packaging material consisting of a layered layer of a low-density homopolyethylene resin extrudigon adhesive layer (outer side) of a horizontally uniaxially stretched high-density polyethylene resin film (outer) with a thickness of 25-2 and a stretching ratio of 6 times. It is. The packaging material for the packaging bag corresponds to FIG. This packaging bag is also ISO
No mold growth was observed using the R846 test method, and waterproof, moisture-proof, and oxygen barrier properties were reliably ensured. The water vapor permeability was less than Ig/rrl for 24 hours.

Inventive product ■ A polyolefin resin layer with a thickness of Son consisting of the same polyolefin resin composition as the inventive product ■, and the old one is 1.0 g/1
96.895% by weight of ethylene-butene copolymer resin with a density of 0.890g/cd and a crystallinity of 38%.
, average particle size 21u, pH 8.0, 3% by weight furnace carbon black with volatile content of 0.8% by weight or less, tetrakis[methylene-3-(3,5-sheet t-butyl-4-
Hydroxy-phenyl)propionate comethane 0.1
Weight%, 2-(4-Th1ayolyl)-Ben
gtmfdazoleO,005 heavy lid % thickness 2
5. This is a packaging bag for long-term storage of prints using a light-shielding blocking laminated film with a thickness of 150 knots, which is made by laminating thermoplastic resins of a light-shielding two-layer coextruded blown film of thermoplastic resins by blocking. A sectional view of the layer structure of the packaging material for the packaging bag corresponds to FIG.

This packaging bag showed no mold growth according to the ISOR846 test method, and its sealability was reliable. Water vapor permeability is 3.1g/
It was 24 hours.

Inventive product ■ The innermost layer is the same mold-resistant polyolefin resin layer 50n as the innermost layer of Inventive product I, with a thickness of 1
This is a packaging bag for long-term storage of prints using a packaging material in which a 15n thick vinylidene chloride surface-coated two-wheel stretched polyester resin film is laminated via a 5n low-density homopolyethylene resin extrusion adhesive layer. The packaging material for the packaging bag corresponds to FIG.

This packaging bag also showed no mold growth according to the ISOR846 test method, and had excellent waterproof, moisture-proof, and oxygen barrier properties.

The water vapor permeability is 4.1g/nf・24 hours, and the oxygen gas permeation rate is 1lcc/rr?・24 hours・Atmospheric pressure (20
゛C・0%RH). Haze was 15%.

Invention Product ■ The innermost layer contains 0.03% glycerin fatty acid ester antifogging agent, 0.05% by weight of erucic acid amide, and n-octadecyl-3-(4''-hydroxy-3°, 5°-di-t). Ethylene containing 0.05% by weight of -butylphenol)propionate and 0.1% by weight of synthetic silica, with an Ml of 2.2g/10 min, a density of 0.922g/aj, and a crystallinity of 43%.
A 50n-thick mold-resistant polyolefin resin layer containing 0.08% by weight of a mold-generating substance made of 4-methylpentene-1 copolymer resin, a 15n-thick maleic anhydride-grafted polyethylene resin intermediate layer, and nylon 6 and nylon 66. Nylon resin manufactured by Mitsubishi Kasei, which is thought to be a copolymer resin (
After sealing the bottom of the tube of a three-layer coextruded blown film with a thickness of 85 nm, which is made of three thermoplastic resin layers with a thickness of 20 nm and does not contain mold-forming substances and is made of NOVAMID (trade name: NOVAMID "1023CAX)", by heat sealing.
This is a packaging bag for long-term storage of prints, with color prints inserted through the opening at the top and the opening also sealed by heat sealing.

The packaging material for the packaging bag corresponds to FIG.

This packaging bag not only has no visible mold growth according to the 150 R846 test method, but also has a temperature of 30℃ and 90% RH.
Heat seal strength decreases by 10% even after being left for 30 days.
Within this range, waterproofness was reliably ensured.

Haze is 18% and water vapor permeability is 8g/rr?・
24 hours, and the oxygen gas permeation rate was 17cc/rrf・
The temperature was 24 hours at atmospheric pressure (20° C., 0% RH).

Invention product■ Thickness: 20. 20% by weight of a commercially available vinylidene chloride coated biaxially oriented polypropylene film coated on one side with a modified polyolefin resin (Mitsubishi Chemical Industries KK Seikagaku brand name: Tubatic AP)
, old is 6 g/10 min EEA resin 10% by weight, phenolic antioxidant (Ciba Kaigy Co., Ltd. product name IRGANO)
X 1010) 0.1% by weight, 2-H of ultraviolet absorber
ydroxy-4-n-octyl-benzophe
None O, 25% by weight, 0.3% by weight of stearic acid monoglyceride as an antifogging agent, 0.3% by weight of polyoxyethylene phenol ether, 5.1 g/
10 minutes, using a packaging material consisting of a laminated film with a thickness of 10 nm laminated with a low-density homopolyethylene resin extrusion coating layer 50Q with a density of 0.919 g / d,
This is a transparent packaging bag for long-term storage of prints, in which a color print is inserted through the opening of a flat bag that is sealed by heat sealing on three sides, and then the print inside the bag can be viewed from outside the packaging bag whose opening is also sealed by heat sealing.

This packaging bag also showed almost no mold growth when tested using the ISOR846 test method, and was found to have excellent waterproof, moisture-proof, and oxygen barrier properties.

The haze is 12%, and the water vapor permeability is 3 g/n (・2
The time was 4 hours, and the oxygen gas permeation rate was 6 cc/rd, 24 hours, atmospheric pressure (20°C, 0% R).

These Inventive Products V to Inventive Products ■ are placed in the metal can that contained the confectionery, the fitting part is sealed with cellophane tape, and a self-regenerating low-temperature unit using an electronic refrigeration element and a desiccant is constructed. The samples were stored in a commercially available low-temperature, low-humidity storage with temperature set at 5-10° C. and humidity set at 20-50% RH.

Comparative product Heat seal layer carbon, LDPE film with lubricant 70
, n/PH adhesive layer 15n/aluminum foil 74/EVA
Layered structure of latex adhesive 3.5N/modified starch, alkyl ketene dimer, and 60N neutral kraft paper.

In this packaging bag, according to the ISOR846 test method, not only did the LDPE film layer and the neutral paper have a lot of mold, but the aluminum foil corroded and holes were formed. The water vapor permeability was 12.6 g/rd・24 hours.

〔effect〕

By configuring the present invention as described above, it is possible to prevent the growth of mold and preserve prints and the like stored in a good condition for a long period of 10 years or more.

[Brief explanation of drawings]

1 to 14 are partial cross-sectional views showing the layer structure of an embodiment of the packaging bag according to the present invention. FIGS. 15 and 16 are cross-sectional views showing an embodiment of a packaging bag according to the present invention having a haze of 80% or less. 1.1a...Mold-resistant polyolefin resin layer a...
Patent applicant indicating that it contains a light-blocking substance Fuji Photo Film Co., Ltd. Agent Patent attorney Japan-China Political situation Haka 1 person Go to Figure 2-h-1

Claims (9)

[Claims] (1) Print long-term storage packaging characterized in that the innermost layer is a mold-resistant polyolefin resin layer containing 5% by weight or less of mold-generating substances and 5% by weight or more of ethylene copolymer resin. bag (2) The packaging bag for long-term storage of prints according to claim (1), which has at least one light-shielding layer. (3) The packaging bag for long-term storage of prints according to claim (1), which has a haze of 80% or less. (4) The packaging bag for long-term storage of prints according to claim (1), which has a moisture permeability of 10 g/m^2.24 hours or less and an oxygen permeability of 100 cc/m^2.hr.atm or less. (5) Add 1 or more fungicide to the mold-resistant polyolefin resin layer.
The packaging bag for long-term storage of prints according to claim (1) containing 1000 ppm. (6) The packaging bag for long-term storage of prints according to claim (1), wherein the mold-proof polyolefin resin layer is sterilized. (7) The packaging bag for long-term storage of prints according to claim (3), which contains an antifogging agent. (8) The print is sealed in the packaging bag for long-term storage of the print according to claim (1), and the temperature is 23° C. or lower and 70% RH.
A long-term preservation method for prints characterized by maintaining them in the following conditions: (9) 5 to 95% by weight in the mold-resistant polyolefin resin layer
Claim (1) containing high-density polyethylene resin of
Printed long-term storage packaging bags listed in