JPS63213585A - Packaging material for photosensitive material enabling safe storage of said material from viewpoint of photographic characteristic - Google Patents

Abstract

PURPOSE:To obtain a packaging material for photosensitive material capable of safely storing a photosensitive material over a long period without causing fogging, etc., by using an adhesive containing a specific amount of a specific compound. CONSTITUTION:The objective packaging material for photosensitive material is produced by using an adhesive having excellent adhesivity and processability and produced by compounding (A) one or more compounds selected from oxides, hydroxides, carbonates, bicarbonates, chlorine compounds, bromine compounds, phosphoric acid compounds, boric acid compound, aluminic acid compounds, silicic acid compounds and organic acid compounds of the group I atom. (excluding H), group II atom., B, Al, Pb, Cr, Mn, Co or Ni of the periodic table to (B) an adhesive resin component (preferably high-density polyethylene, etc.) in an amount of 0.1-2wt.%, preferably 0.8-1.3wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a packaging material for photographic light-sensitive materials, and more specifically, the present invention relates to a packaging material for photographic light-sensitive materials, which can be safely stored for a long period of time without causing an increase in fog on the photographic light-sensitive materials, and which has adhesive properties, This invention relates to a packaging material for photographic materials using an adhesive with excellent processability.

[Background of the Invention] Adhesives are used in various forms in packaging materials for photographic materials. For example, adhesives for locking photographic film and spools, adhesives for pasting labels etc. on cartridges, pairing adhesives used for 120 size film (Brownie), etc. 49
No. 32, No. 60-208751, No. 61-21034
No. 7, No. 61-233738, No. 61-289347
Adhesives for pasting light-shielding cloth on batonets and magazines, as described in JP-A No. 56-32139,
No. 57-6754, No. 57-38134, No. 58-
No. 132555, No. 59-68238, No. 59-2
No. 01848, No. 60-8393, No. 60-15
No. 1045, No. 60-189438, No. 60-19
No. 6335, No. 60-244533, No. 61-64
No. 438, No. 61-78635, No. 61-54934
No. 61-110541, No. 61-237640
Barrier materials described in No. 62-18546, No. 62-18-47, etc., adhesives used for laminating layers constituting light-shielding paper, etc., resins for heat-sealing adhesives, etc. .

When considering and exploring the use of such adhesives, the main condition is that there are no problems in terms of photographic performance, including adhesion strength, workability, and cost. Among packaging materials for photographic light-sensitive materials, many adhesives have a negative effect on photographic performance compared to other materials, and there are very few adhesives that can satisfy the above-mentioned conditions. In particular, thermoplastic adhesives, due to their characteristics, are often heated in application equipment like solution tanks, and in such cases, for example, low molecular weight tackifiers may deteriorate due to heating time and temperature. Previous experiments have confirmed cases in which substances that pose problems in photographic performance are released as a result. Therefore, even if the adhesive has no problems in terms of photographic performance, its photographic properties may change completely due to deterioration during the coating or bonding process.

As described above, adhesives involve problems in photographic performance more than other photographic packaging materials, and the factors and mechanisms that cause problems in photographic performance are still not fully understood. Since there are many unresolved issues, it has taken a great deal of time and money to search for and study adhesives that meet these conditions and have excellent adhesion, processability, etc.

The present inventors have developed a packaging material for photographic materials that prevents adverse effects such as increased fog on the photographic material from the packaging material, as well as deterioration of the material over time, by allowing a specific compound to exist near the photographic film. Special request for method
No. 0-282627, No. 60-282628, No. 6
No. 0-282629, No. 61-153880, No. 6
No. 1-153881 and No. 61-189425.

In the above, especially for adhesives, in consideration of the decrease in their adhesive strength, it is proposed that it is preferable to mix them into packaging material components other than adhesives or to make them exist independently in the vicinity of photosensitive materials. However, it has been found that such a method of indirectly acting on the adhesive is not yet sufficient in preventing the adhesive from adversely affecting photographic performance. On the other hand, the method of directly mixing a specific compound with anti-fogging ability into an adhesive has an excellent anti-fogging effect, but it also reduces the adhesive properties of the adhesive and has poor processability. Such problems arose, and it could not be said that the overall problems regarding adhesives had been solved yet.

[Object of the Invention] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to enable safe storage without causing an increase in fog etc. on the photographic materials to be stored, and to provide adhesive An object of the present invention is to provide a packaging material for photographic materials using an adhesive that does not deteriorate its original function.

[Structure of the Invention] The above-mentioned object of the present invention is to provide a packaging material for a photographic light-sensitive material for storing a photographic light-sensitive material, in which the adhesive used in the packaging material is a group 1 group excluding hydrogen atoms in the periodic table of elements and Group ■ atoms and 81AI, Pb, Cr, Mn
, oxides, hydroxides, carbonates, hydrogen carbonates, chlorine compounds, bromine compounds, phosphoric acid compounds, boric acid compounds, aluminic acid compounds, silicic acid compounds and organic acid salts containing selected rel atoms from Go and Ni, respectively. This was achieved by a packaging material for photographic materials containing at least one compound selected from the group of compounds consisting of 0.1% by weight or more and less than 2% by weight based on the adhesive resin component.

[Specific structure of the invention] The compound used in the packaging material for photographic light-sensitive materials of the present invention (
(hereinafter referred to as the compound of the present invention) is a group I group excluding hydrogen atoms, that is, Li, Na, Rb, C3, CLI, A
(Each atom of l; group ■, i.e., Be, Mg, Ca, 5r1B
a, Zn, Cd, l-1q atoms, and BlAff
i, Pb, Cr, Mn, C.

It is a compound containing each atom of and Ni.

The compound of the present invention is a compound containing the above atoms, and its compound forms include oxide, hydroxide, carbonate, hydrogen carbonate, chlorine compound, bromine compound, phosphoric acid compound, and boric acid compound. , aluminate compounds, silicate compounds and organic acid salts.

Although the compound of the present invention includes all of the above-mentioned compound forms containing the above-mentioned atoms, specific examples of preferred compounds are shown below.

Oxides of the following atoms: Li, Be, Mq SCa, Ba, 8% Af
fi, Zn, Cd, Pb, Cu', Ag, Cr, Mn,
o1Ni Hydroxide of the following atoms: Li 1Na, Mg, Ca, Sr, Ba.

Zn, Cd, AffiSC.

Carbonates of the following atoms: Li, Na, Ni, Rb, Cs, M(+, C
a.

Sr, Ba, Zn, Cd, Cu, AoSPb.

Mn, C0 Hydrogen carbonates of the following atoms: Na, chlorine compounds of the following atoms: Li, M(J, Ca, Ba, Cu,
Bromine compounds of atoms below Cd, Pb: M(+, Ca, Sr, Zn, Cd XC.

Phosphate compounds of the following atoms: Na, ni, c.

Boric acid compounds of the following atoms: Na, Mn Aluminate compounds of the following atoms: Na, silicic acid compounds of 38 or less atoms: MIJ, Ca organic acid salts: Acetate salts of the following atoms: Li, Na, KqCa, M (1,5r-Zn, in addition to the compounds exemplified above, for example, CaO・n Ae203
．． Chemical compounds such as 2Ctl (OH)2 and CoO.ZnO are also included in the compounds of the present invention.

The compound of the present invention is used by being added to the adhesive resin component, but especially when the adhesive resin component is thermoplastic, most of them are subjected to temperatures of 100°C or more during processing.
The compound of the present invention may release moisture and generate bubbles in the adhesive, reducing adhesive strength or causing uneven coating. The following compounds are preferably used:

tvlo %Ca %Sr, Na, Affi,
7-oxides, hydroxides, carbonates, aluminate compounds containing atoms selected from n, co and Mn, respectively;
silicic acid compounds, and stearic acid compounds.

Furthermore, the most preferable compounds as compounds that are free from deliquescent properties and efflorescent properties, have low moisture absorption properties, are inexpensive, and are excellent in the effects of the present invention are as follows.

Oxides containing the following atoms: Ca, Mo, C.

Hydroxide containing the following atoms: Ca, M (1, Aj!
, Zn, Q.

Carbonates containing the following atoms: Mg, Sr, 7-n, M
n, G.

Sodium aluminate, magnesium silicate, calcium silicate, sodium stearate, and magnesium stearate The above compounds of the present invention may be used alone or in combination of two or more kinds, and roughly include double salts.

The compound of the present invention is used in an amount of 0.1% by weight or more and less than 2.0% by weight based on the adhesive resin component. Taking into account the decrease in adhesive strength as an agent (including the decrease in adhesive strength due to aging and durability tests, etc.), it is preferably 0.5% to 1.5% by weight, more preferably 0.
．． It ranges from 8% to 1.3% by weight.

The adhesive resin used in the present invention can be used without particular limitation as long as it has adhesive strength, and representative examples include polyolefins such as high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, etc.
Polyvinyl such as vinyl acetate and vinyl chloride, nylon 1
2. Polyamides such as nylon 10 and nylon 6, polyesters such as polyethylene terephthalate and polyethylene isophthalate, acrylics such as acrylic esters and methacrylic esters, polycarbonates, cellulose, butadiene, chloroprene, styrene, etc. alone or Copolymers such as synthetic rubber, polyurethane, epoxy, and ionomer resins, as well as ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, styrene-butadiene copolymer, styrene-acrylic ester copolymer, butadiene-methyl methacrylate copolymer , acrylonitrile-butadiene copolymers, which may be used alone or in combination.

In the above-mentioned adhesive resin component, materials more preferably used in view of the effects of the present invention include the polyolefin type, polyvinyl type, polyester type, synthetic rubber type, acrylic type alone, coboryl, styrene-butadiene copolymer, These are ethylene-vinyl acetate copolymers and various acrylic polymers alone and mixtures.

The method of adding the compound of the present invention to the above adhesive resin is not particularly limited, and specifically, the compound of the present invention may be added in advance during the adhesive resin manufacturing process, or mixed after the adhesive resin is manufactured (for example, adhesive A method such as kneading the compound of the present invention with an adhesive resin to a concentration of 50 gm or less to form a masterbatch, and then diluting it to the concentration range of the present invention), and further melting of the adhesive resin before application. Methods include adding directly into a tank or supply tank.

Typical examples of adhesives used in the packaging material for photographic materials of the present invention include adhesives for locking photographic film and spools, adhesives for pasting labels etc. onto cartridges, etc., and 120 size adhesives. Pair adhesives used for films (Brownie), etc., adhesives for pasting light-shielding cloth on cartridges and magazines, barrier materials, adhesives used for pasting each layer of light-shielding paper, etc., and resins for heat-sealing. etc.

Therefore, the form of use of the adhesive used in the present invention is not particularly limited (it may be appropriately selected depending on the application. It is typically applied with a film thickness of about 5 μm to 300 μm, but Kaisho 57-6754, 60-24
No. 4533, No. 61-64438, No. 61-7863
It is also possible to form a layer in a special shape as described in No. 5, No. 61-110541, and the like.

As a means for applying the adhesive, for example, a roll coater, a curtain 70-coater, an extrusion coater, various hot melt applicators, etc. can be arbitrarily used.

In addition to the compound of the present invention, additives that are normally added to adhesives can be optionally added to the adhesive used in the present invention. In addition, in order to provide light shielding and properties, various carbon blacks (e.g. conductive carbon blacks such as oil furnace black, acetylene black, and Zarani Kejien carbon black, etc.), metal powders, and various pigments (particularly, Chrome Yellow described in No. 61-189425, Ri0
Movermillion, soluble azo pigments, quinacridone pigments, isoindolinone pigments, LF Red 4R pigments, etc. improve the reliability of the effect of the present invention on photographic performance. ) can also be added.

The photographic material to which the packaging material using the adhesive containing the compound of the present invention is applied is any photographic material, such as X-ray photographic material, lithographic photographic material for printing, black-and-white photographic material. Examples include light-sensitive materials, color photographic materials, and other photographic materials.

[Specific Examples of the Invention] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 In a 135 photographic film magazine, Teremp (pile fiber: nylon 6,6, base fabric fiber: rayon) was added to the magazine body, and calcium hydroxide was contained as an adhesive in the content shown in Table 1 below. Samples Nos. 1-1 to 1-8 were prepared by adhering them using an ethylene-vinyl acetate copolymer.

Table-1 Example-2 Samples Nos. 2-1 to 2-2- 15 was created.

Table 2 Example 3 Sample No. 1 was prepared in the same manner as Example 1 except that the adhesive resin shown in Table 3 below was used instead of the ethylene-vinyl acetate copolymer in Sample No. 1-5.

3-1 to 3-4 were created, and sample No. 3-1 to 3-
Samples Nos. 3-5 to 3-8 were prepared in which no calcium hydroxide was added.

Table 3 Example 4 As a hot-melt adhesive used for 12G paper seals, ethylene-vinyl acetate copolymer with and without 1% calcium hydroxide added was used in an extrusion coater. Sample N
o, 4-1 and 4-2 were created.

Example 5 As a barrier material in which the laminated materials shown in Table 4 below were laminated, samples No. 5-1~5
-5 was prepared, and sample no.

In 5-1 to 5-5, calcium hydroxide was added. In Examples 1 to 4, Sakura Color SR-400 film was used as the interior, and in Example 5, Saheshi X-ray-8 type film was used as the interior. .

Regarding the above samples, the samples of Examples-1 to 4 were heated at 60℃3
In Example 5, thermoprocessing was performed at 50° C. for 3 days, and the film sample after thermoprocessing was developed and the fog density was examined. At this time, as a control sample, only the film was thermotreated in the same manner as above and the fog density was measured. In Examples 1 to 4, each of blue, green, and red fog densities were measured, and in Example 5, monochrome fog density was measured using the following criteria.

Examples-1 to 4 (all B, G, and R) 0... Control sample + 0.01 or less Δ... Control sample +
0.01-0.05×...Control sample +0.0
5 or more Example-5 0... Control sample + 0.01 or less Δ... Control sample + 0.01 to 0.02 ×... Control sample + 0.02 or more Adhesive properties are measured based on the samples to which no compound is added, A: 1 hour after adhesion, B: 70' after adhesion.
C: after treatment for 20 days, and C: after treatment at 45°C and 90% relative humidity for 30 days after adhesion, the rate of decrease in adhesive strength was measured using the following criteria.

○・・・Less than 10% Δ...10-30% ×・・・Over 30% The above results are summarized in Tables 5 and 6.

Table 6 (X-ray-A film) From the results in Tables 5 and 6, various photographic material packaging materials using adhesives containing the compound of the present invention within the scope of the present invention can be It can be seen that under all conditions, there was no adverse effect on photographic performance and the adhesive properties were excellent.

Claims (1)

[Claims] In a packaging material for a photographic light-sensitive material that stores a photographic light-sensitive material, the adhesive used in the packaging material contains atoms of Groups I and II in the Periodic Table of the Elements excluding hydrogen atoms, and B
, oxides, hydroxides, carbonates, hydrogen carbonates, chlorine compounds, bromine compounds, phosphoric acid compounds, boric acid compounds, and aluminate compounds containing atoms selected from , Al, Pb, Cr, Mn, Co, and Ni, respectively. , 0.1% by weight or more of at least one compound selected from the group consisting of silicic acid compounds and organic acid salts based on the adhesive resin component2.
A packaging material for photographic materials, characterized in that the content is less than % by weight.