EP0846077B1 - Package for moisture-sensitive unexposed film material - Google Patents

Description

The invention relates to a packaging for moisture-sensitive Good, especially for photo footage consisting of Wall and cover parts and an interior enclosed by them.

A container in the lid of a moisture-permeable film is incorporated to the unwanted impairment of vegetables to avoid condensation during storage in the refrigerator door, is described in EP-A-0 240 955.

From US-A-4 903 834 is a multi-layer, moisture permeable Packaging, known for heat and light sensitive Diazo material, the effect of increased humidity, such as Example if the packaging is heated to more than 50 ° C, unfolded.

Photo films, in particular 35 mm, negative or positive films are made by the film manufacturers in plastic cans with lids packed for vapor-tight storage. According to US 4,639,386 there is such a plastic can e.g. from a polymer Resin that contains mostly polypropylene and a little Moisture permeability of 2.3 mg / on the 1st day of a series of tests owns.

DE-OS 40 14 680 is a packaging for a 35 mm plastic box known in a water vapor tight, e.g. out aluminum foil coated on both sides, weldable Bag is included.

With the DE-GM 94 07 945 (O.Z. 0078/06175) the applicant is a Containers for photo film, consisting of cardboard, paper and / or Plastic material or a multi-layer composite material known, preferably by means of an interposed heat seal film the container parts are connectable to the additional Advantage of water vapor impermeability or a To achieve moisture protection from the outside.

The can and container designs described above have that common goal of achieving tropical suitability for Protection of the film, i.e. protection against the ingress of Moisture from outside.

However, the photo film materials change under different Climates their properties, especially the sensitometric ones. In addition, high humidity leaves the film, combined with high Temperature, age faster. This aging process can go so far go that e.g. in the case of color negative photo films, the negatives are not are more copyable and thus useless.

Because the photo films through their manufacturing process a certain A moisture-proof packaging can have residual moisture accelerated aging when stored in the warm lead what is known and against a tempering of the film material after the manufacturing process by some film makers is made. A possibly related artificial one Aging of the film material must then be accepted.

Annealing or tempering is understood to mean that after production part of the film's residual moisture is expelled and the remaining moisture is evened out over the film layers becomes.

With EP-A 476 535 it is also known to copy before Silver halide photographic material containing gelatin on a Maximum percentage of 14 percent by weight based on the weight of gelatin, pre-dry to get excellent photographic results to obtain.

It is an object of the present invention to provide packaging create, in which the vapor pressure arising in the interior at least is partially dismantled.

The task comes with a packaging for moisture sensitive Good, especially for unexposed photo footage, consisting of a closed interior and surrounding Wall` and cover parts, solved in that the wall and / or Cover parts at least partially permeable to moisture and / or are designed to store moisture, so that a Can equalize or reduce vapor pressure from the inside.

This saves annealing in accordance with the prior art and an associated artificial aging of the Film material is avoided.

In an expedient design of the packaging, the at least partially moisture-permeable or storage Part within 6 days at a heater temperature from 50 ° C, 20% RH an amount of liquid from about 10 to about 80 mg can escape or be absorbed.

This specifies an area in which the sensitometric, partly due to aging and influencing the copying process Properties of the photo film largely unchanged can be kept, even with long-term storage under tropical conditions.

In practical training, the packaging consists of a can with lid, with at least one escape opening for moisture is provided. This makes it possible to reduce the effort for the To keep the realization of the inventive packaging very low. In addition, the escape opening is available on existing cans to be retrofitted. It is also advantageous to use the escape opening through a cover, especially one from the inside out vapor-permeable film on the outside, cover.

The escape opening can expediently be provided in the cover.

It is also possible to separate the escape opening (s) between Can and lid, especially at the edge of the can or lid, to be provided.

An escape opening can also be provided in a wall of the can his.

With a packaging according to the state of the art, with the wall and Cover parts have a prism shape, the attachment of the escape opening advantageously possible on at least one wall part.

It is also appropriate to use the material of the can, lid or Form prism container wall parts to be moisture-permeable.

Further training is provided if cover means are provided are, by means of which the escape opening at least partially can be covered.

Moisture-proof packaging is feasible if the same at least partially from hygroscopic material exists or is located on wall or cover parts. The subject of the invention is also a packaging according to the invention with at least one movie in it.

Embodiments of packaging according to the invention are in the Drawing shown and below using comparative examples described.

Figur 1

eine Verpackung als Zylinderdose mit Deckel

Figur 1 A

ein Längsschnitt durch die Dose mit Deckel aus Figur 1

Figur 1 B

eine Draufsicht auf den Deckel

Figur 1 C

ein Deckel mit einer Mehrzahl von Entweichöffnungen und getrennt dargestellter Abdeckung dafür

Figur 1 D

der Deckel mit angebrachter Abdeckung aus Figur 1 C.

Figur 2

eine Quader- oder Trapezform-Dose

Figur 3

eine in Draufsicht Fünfeck-Form-Dose

Figur 4

eine in Draufsicht Dreieck-Form-Dose

Figur 5

ein Wandteil mit integrierter Durchlässigkeitsstelle oder Speicherstelle

Figur 6 - 8

ein Prismen-Form-Behälter mit Durchlässigkeitsstellen oder Speicherstellen

Figur 9

eine Zylinderdose

Figur 9 A

eine Version mit Öffnungen zwischen Dosenrand und Deckel

Figur 10

ein Deckel mit 2 Entweichöffnungen, einer Durchtrittsöffnung und einer Abdeckscheibe

Figur 10 A

den Deckel und die Abdeckscheibe aus Figur 10 im Querschnitt

Diagramme A1, A2, B1 und B2

Gradations- und Dichtekennwerte von Filmen A bzw. B in Dosen nach Heizschranklagerung

The drawing shows in

Figure 1

a packaging as a cylinder jar with a lid

Figure 1A

2 shows a longitudinal section through the can with a lid from FIG. 1

Figure 1B

a top view of the lid

Figure 1C

a cover with a plurality of escape openings and cover shown separately

Figure 1 D

the lid with attached cover from Figure 1 C.

Figure 2

a box or trapezoidal shape box

Figure 3

a pentagon shape can in plan view

Figure 4

a top view triangle shape can

Figure 5

a wall part with an integrated permeability point or storage point

Figure 6-8

a prism-shaped container with permeability or storage locations

Figure 9

a cylinder can

Figure 9 A

a version with openings between the edge of the can and the lid

Figure 10

a lid with 2 escape openings, a passage opening and a cover plate

Figure 10 A

the cover and the cover plate from Figure 10 in cross section

Diagrams A1, A2, B1 and B2

Gradation and density parameters of films A and B in cans after storage in the heating cabinet

The cylinder boxes 5 with lids 6 according to FIGS. 1, 1 A and 9 are of known outer form.

The cover 6 according to FIG. 1 has a plurality, in particular 6, of circular openings 7 with a diameter of about 1 mm or trained smaller. It is, as in the following experimental examples, also a hole with 2.5 - 3.5 mm can be used, which at 2.5 mm even the total area of the 6 holes of 1 mm diameter approximately corresponds.

The cover 8 in Figures 1 C and 1 D can e.g. made of plastic film material exist, the only one-sided for water vapor is permeable or made of another material with the finest Openings through which the water vapor pressure can escape. The Openings 7 in Figure 1 D can also be made by a suitable, partially permeable Self-adhesive film 8 A must be covered. The cover 8 can also be suitably clamped in the cover 6. In the figures 2 to 4 are each a zone 15 of the lid 9-10 of the cans 12 to 14 water vapor permeable, of course can instead of the lid parts (or) also the wall parts of the cans 12 to 14 with arbitrarily shaped through openings or - Places 15 A in Figure 3 be of a suitable size.

In Figures 6 to 8 are prismatic containers 16 to 18 with flat extensions shown for film ends. Permeability zones 19 are at 16 on a face 20 of the roof prism, at 17 a side surface 21 of the cuboid prism and on the top 22 of the trapezoidal shape prism provided.

FIG. 5 shows an arbitrary wall or cover section cutout 23 with a permeability or storage location 24 or 25. As Permeability point can e.g. in the area of position 24 one special coating present or not present in order to create the desired permeability. As a storage location 25 can e.g. a hygroscopic substance on this spot be plotted, the absorption capacity of the dispensed Amount of liquid should correspond approximately.

FIG. 9 A shows as fine grooves 26 on the upper edge 27 of the can 5 trained escape openings under the lid edge 23. The number and formation of the grooves 26 can be suitably dimensioned. Of course, the inner part of the lid edge 28 is also included Grooves or ribs with a smooth upper edge 27 of the can 5 trainable.

Figure 10 finally shows a cover part 29 with escape openings 30 and a passage opening 31 and a flat turntable 32 with sector permeability points 33 and a pivot 34. In Figure 10 A is the cover part 29 with the cover plate 32 shown in cross section.

As indicated by dashed lines, the pivot pin 34 passes through one Passage opening 31, and the turntable 32 is on extensions supported. In this version it is possible to open or To close or open openings 30 or also partially to open. When the film content is exposed, a closed Position of the disc 32 is also an identifier for the Exposure state.

Woven, knitted or nonwoven films which have a basis weight of approximately 100-180 g / m ² and a fiber thickness of approximately 10 μm to approximately 25 μm are suitable as a vapor and / or gas-permeable cover for the escape opening (s) , with fiber weights from approx. 1.5 to approx. 5 g / 10,000 m. Synthetic fiber papers can also be used.

The following were specific in the examples (table on page 9) Cover materials used:

L₁

eine Azetatseiden-Folie mit Kleber

L₂

ein Kunstfaser-Papier (der Bezeichnung "Fiberstock")

L₃

eine Azetatseiden-Folie mit Kleber (Typ 80120 der Firma Jackstätt GmbH, Wuppertal) mit einem Flächengewicht von etwa 125 g/cm².

At

L ₁

an acetate silk foil with glue

L ₂

a synthetic fiber paper (called "Fiberstock")

L ₃

an acetate silk film with adhesive (type 80120 from Jackstätt GmbH, Wuppertal) with a weight per unit area of approximately 125 g / cm ² .

In principle it is also possible to partially or completely Made entirely from surface-coated paper or cardboard materials to produce, the coating while penetrating prevent or at least reduce moisture from outside should and the paper or cardboard material and the coating should be permeable to moisture from the inside out.

The moisture absorption capacity of paper and / or Cardboard materials are used.

With moisture-storing chemical materials, e.g. as a layer in whole or in places on the inner wall and / or Parts of the cover can be attached, there are hygroscopic chemicals, the harmless in connection with photo film materials are in question.

Such chemicals form with moisture e.g. solid components, which you remove from the packaging after use can.

Of course, paper or cardboard materials are also moisture-storing, provided it is made from natural cellulose are.

It was the behavior of commercially available color negative films tested by various manufacturers for storage in a cabinet. The Films A to F were all 100 ASA films, which are also material were comparable.

While at normal temperatures (20 ° C) and a relative Moisture (RF) of 55 - 60% hardly any moisture escape from the Footage that can be observed decreases depending on the temperature increase this increases sharply and can be very dense closing lid boxes to a microclimate within the lid box lead, which the sensitometric properties of the Film can have a lasting negative impact.

Storage temperatures of 40 ° C, 75% RH and 50 ° C were examined, 20% RF over a period of up to 22 days. These storage conditions make realistic variants in practice , taking into account the temperatures in southern countries, unclimatized storage rooms and transports, vacation trips with the Cars in summer etc.

Carrying out the experiments:

After a 6-day adaptation of the films (brands) A - F in sealed standard lid cans to the laboratory environment were the Films with the sealed lid cans weighed using a Weighing apparatus (electronic balance, type Sartorius handy H 51).

Then the standard lid boxes were opened in the heating cabinet placed and after the 7th, 15th and 22nd day after removal closed and weighed and then opened again in the Heating cabinet.

Results:

• During the six-day adjustment phase (natural storage) there was only a very small loss of mass, accordingly water loss.
• The mass loss in the heating cabinet took place at elevated temperature after initial strong change in asymtotic Approaching the final value. The samples differ in terms of of mass loss strong.
• The rate of mass loss is also temperature dependent. At 40 ° C storage will take about 14 days and at 50 ° C storage less than 7 days needed to get the final value to reach. The materials examined differ here barely.
• When examining the acetate film base, a clear Relationship between the residual solvent content the pad and the mass loss that occurred become.

The average change in mass of films AF resulted in to at 40 ° C [mg] at 50 ° C [mg] 7 days - 170 - 282 15 days - 233 - 278 22 days - 235 - 289

It can therefore be assumed that depending on the duration storage and heating cabinet temperatures depending on the film brand between 170 and 290 mg water and other liquid or gas components emerge from the base and emulsion, the negative Influences on the film parameters, gradation, minimum density and Can exert sensitivity of the film.

In order to determine such influences, said characteristic values for determined the film A.

Films A were closed in standard, sealed, lidded cans Hole and in lid boxes with a hole of 3 mm diameter 14 days in Heating cabinet stored at 50 ° C, 20% RH. It was found that in all cases with perforated lids that are photographically effective sensitometric changes are smaller than in Storage in the tightly closed standard lid box.

Film A had a particularly negative effect on the increase in fog (increase in minimum density) and the decrease in the blackening curve (flattening of the gradation curve), as well as the sensitivity to casting (which has an effect as a strong color shift to blue). parameter colour Values fresh Values after 14 days in the cupboard with a hole Rifle without hole not annealed post-annealed not post annealed post-annealed Minimum density blue 0.64 0.72 0.69 0.82 0.70 green 0.52 0.58 0.56 0.69 0.59 red 0.11 0.16 0.15 0.30 0.17 gradation blue 0.72 0.66 0.68 0.63 0.66 green 0.60 0.54 0.56 0.47 0.55 red 0.59 0.52 0.54 0.42 0.52 ISO blue 22.9 24.7 24.2 24.9 24.7 green 21.5 21.4 21.0 20.0 20.2 red 20.0 20.5 20.0 20.0 20.2

Tempering the Film-A material before closing the standard lid box causes a significant reduction in changes the sensitometric parameters during storage in the heating cabinet.

It can be observed that the complex tempering and a Hole in the lid box after 14 days in the heating cabinet show equally large effects, while normally made-up materials (without tempering in the tight standard lidded box) one show significantly higher deviation from the values when fresh.

The further experiments with partially permeable film labels and a hole with a diameter of approx. 2.5 - 3 mm are the following remove.

Change in mass of differently packaged films (brands A and B) in the heating cabinet. Temp .: 50 ° C, RH = 20% Storage period / days 0.9 6.0 8.1 12.0 15.2 sample material Pretreatment Mass change (mean) / mg 2nd Film A not annealed -2.4 -9.9 -13.4 -18.3 -23.1 4th Film A not annealed -2.7 -10.8 -14.6 -19.4 -24.4 6 Film A not annealed -4.1 -16.2 -21.3 -28.1 -34.2 8th Film A not annealed -6.1 -27.7 -36.5 -48.0 -56.9 10th Film A not annealed -44.8 -117.4 -129.0 -126.5 -130.3 12th Film A annealed -26.0 -66.1 -74.8 -70.5 -73.8 102 Film B not annealed -2.4 -10.8 -14.0 -18.7 -23.3 104 Film B not annealed -3.5 -16.0 -20.1 -26.9 -33.0 106 Film B not annealed -6.1 -28.4 -36.4 -48.2 -57.7 108 Film B not annealed -12.3 -56.9 -71.7 -90.3 -103.9 110 Film B not annealed -55.7 -143.5 -153.9 -152.4 -157.2 112 Film B annealed -27.8 -70.5 -77.9 -75.1 -79.0

The following maximum mass change values result:

When evaluating the results of the last table, that the after-drying mass loss (difference from mass loss of the annealed film from the non-annealed film, measured in each case after drying the heating cabinet in an open can) the value of the achieved L3 version hole bulk loss with acetate silk foil cover the closer the longer the duration of the Heated cupboard drying is. Was above when comparing the film A characteristics measured after storage in a cabinet with a not covered hole in the lid box.

The material of the hole cover L3 was an acetate silk film (see p. 6), the one-sided (from the inside) the vapor pressure to the outside allows moisture to enter and from the outside in locks.

In quantitative side analyzes it was demonstrated that the Mass change of more than 90% due to water loss during the drying process arises.

O Film

nicht getempert (Kühllagerung)

1 Film

nicht getempert 14-Tage-Heizschranklagerung 50°C, 20% RH (g)

2 Filme

nicht getempert 14-Tage-Heizschranklagerung 50°C, 20% RH (L1)

3 Filme

nicht getempert 14-Tage-Heizschranklagerung 50°C, 20% RH (L2)

4 Filme

nicht getempert 14-Tage-Heizschranklagerung 50°C, 20% RH (L3)

In diagrams A1, A2 (film A) and B1, B2 (film B), the characteristic values after 14-day heating cabinet storage of the film samples with the hole covers L1 - L3 are compared with those of the film samples in tightly closed lid cans: the numbers indicate this the abscissa:

O film

not annealed (cold storage)

1 film

not tempered 14-day storage at 50 ° C, 20% RH (g)

2 films

not tempered 14-day storage at 50 ° C, 20% RH (L1)

3 films

not tempered 14-day storage at 50 ° C, 20% RH (L2)

4 films

not tempered 14-day storage at 50 ° C, 20% RH (L3)

The numbers on the ordinate mean the gradation or minimum Density difference values related to the 0 state of the film.

Gradation difference values in diagrams A1 and B1.

Minimum density difference values in diagrams A2 and B2.

• ein auf die Spitze gestelltes Quadrat für Blau
• ein normal liegendes Quadrat für Grün
• ein Dreieck für Rot

The following symbols apply to the gradation and minimum density values

• an upside down square for blue
• a normal square for green
• a triangle for red

From diagrams A1 and A2 for film A and B1 and B2 for film B there is the positive influence of the packaging variants according to the invention on the sensitometric values gradation and minimal Density of films A and B as follows.

In the packaging L1 - L3 the influences could on gradation and minimum density of the film material the conventional storage of the unannealed, unexposed Films in standard lids are essentially halved become.

Claims (8)

1. A pack for unexposed photographic film material, which is sensitive to moisture, comprising wall and lid parts (5, 6), and an interior enclosed thereby, wherein the wall and/or lid parts (7, 8, 8A, 15, 15A, 19, 24 and 25) are formed such that they are at least partly moisture-permeable and/or moisture-accumulating, and through which an amount of moisture of approximately 5 mg to 10 mg can escape or be absorbed from inside to outside within one day, an amount of moisture of at least 10 mg can escape and/or be absorbed from inside to outside within 6 days, or approximately 20 mg to 120 mg can escape and/or be absorbed from inside to outside after a period of 15 days at a heating cabinet temperature of 50°C, 20% relative humidity in the case of an unconditioned, unexposed film.
2. A pack as claimed in claim 1, wherein the same comprises a container (5) with lid (6), there being provided at least one opening (7) of 2.5 - 3.5 mm in diameter for the escape of the moisture.
3. A pack as claimed in claim 2, wherein the at least one escape opening (7) is covered by a one-sidedly vapor-permeable film.
4. A pack as claimed in claim 2 or 3, wherein the at least one escape opening (7) is provided in the lid (6).
5. A pack as claimed in claim 2 or 3, wherein escape openings (26) are provided between container rim (27) and lid rim (28).
6. A pack as claimed in claim 2 or 3, wherein the at least one escape opening (15A) is provided in a wall of the container (13).
7. A pack as claimed in any of claims 1 to 6, wherein the wall and lid parts have a prismatic shape (13).
8. A pack as claimed in claim 1, wherein wall and/or lid parts (5, 6) consist of hygroscopic material (25) or there is such material on wall and/or lid parts.

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