JPS6014237A - Photosensitive material packaging material - Google Patents

Abstract

PURPOSE:To obtain a packaging material especially enhanced in an X-ray intercepting function and good in strength and workability by incorporating an X-ray intercepting material, such as Ba, Sn, Zn, Pb or their compds., or a combination of >=1 of them, in a specified amt. range. CONSTITUTION:The packaging material of a photosensitive material is obtained by dispersing particles with 0.2-5mum average diameter of a barium compd. such as barium sulfate or titanate, or proper diameter range particles of Sn, Zn, Pb, or their compds. uniformly into a thermoplastic resin, such as polyoelfin or polystyrene in the range of 50-1,800g/m<2>. As a result, the obtained packaging material is perfect in a light intercepting performance, like a movie film case, improved in workability for simplifying handling of taking out a film, and enhanced in X-ray interception performance, and reduced in weight and cost.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin material for packaging photosensitive materials, and more particularly to a thermoplastic resin material suitable for accommodating photographic film and the like and opaque to light and X-rays.

Conventionally, packaging containers for silver halide photographic materials, especially high-sensitivity films (photography films with ASA 25 or higher) and X-ray films that are prone to fogging due to X-rays,
Metal cans made of tin-plated steel plates, carrier cases made of metal such as aluminum lined with lead, or bags laminated with lead sheets are used. Metal cans have the disadvantage that the external shape is controlled by the required shape of the inner surface, making it difficult to create a suitable external shape for handling, and that it is difficult to mold the surface in a complicated manner, making them slippery and prone to cargo collapse.
The latter two have the drawbacks of being extremely heavy and expensive.

For this reason, attempts have been made to develop packaging materials that reduce costs by mixing large quantities of talc, clay, calcium carbonate, mica, etc. as fillers in thermoplastic resins. However, these large amounts of filler reduce the strength of the thermoplastic resin and impair its fluidity, so when used in containers for storing photographic film, etc., the amount of filler must be kept to a few 2 by weight. I didn't get it. Therefore, when thermoplastic packaging materials are used as containers for photosensitive materials, among the characteristics required for packaging materials for photosensitive materials, such as photographic properties, light opacity, and X-ray opacity, X-ray opacity is sacrificed. It became.

Therefore, an object of the present invention is to provide a thermoplastic resin material for packaging photosensitive materials that has photographic properties, light opacity, and X-ray opacity, and also satisfies strength and fluidity.

Another object of the present invention is to provide a thermoplastic resin material for packaging photosensitive materials for forming an X-ray shielding container with high commercial value as an alternative to conventional packaging containers. The present invention includes a barium compound as an X-ray opaque substance in a thermoplastic resin,
A thermoplastic resin material for packaging a photosensitive material is provided, which contains 50 to 1800 g/rn' of zinc or a zinc compound, tin or a tin compound, and lead or a lead compound.

In the present invention, polyolefin resins, polystyrene resins, ABS resins, etc. are used as thermoplastic resins. As the polyolefin resin, various polyethylenes, copolymers thereof, various polypropylenes, copolymers thereof, or mixtures of these resins and other thermoplastic resins are used. As the polystyrene resin, various polystyrenes, copolymers thereof, and mixtures of these resins and other thermoplastic resins are used. ABS resins include various ABS resins and copolymers thereof.

Alternatively, mixtures of these resins and other thermoplastic resins are used.

In the present invention, the amount of barium compound etc. added to the thermoplastic resin is 50 to 1800 g/rn', preferably 100 to 1000 g/rn', most preferably 200 g/rn'.
~600g/rn'. If the amount is less than the above lower limit, the X-ray transmittance will increase, while if the amount is more than the above upper limit, the strength and fluidity will be impaired, making it unsuitable as a material for packaging photographic materials.

As barium compounds, barium sulfate, barium chloride, barium hydroxide, barium titanate, etc. can be used, as zinc compounds, zinc oxide (zinc white), complexed zinc, etc. can be used, and as tin compounds, tin oxide, etc. can be used. As lead compounds, lead oxide, graphite, lead potassium silicate, etc. can be used. In the case of barium compounds, these radiopaque substances have an average particle size of 0.2 to 5 pLm, preferably 0.5 to 2 g.
m, in the case of zinc, the average particle size is 90 pm or less, preferably 89
Bm or less, in the case of tin, 60pLI11 or less, preferably 50
pL 11 or less, in the case of lead 180gm or less, preferably 10
It is made into granules of less than 0 gm.

The above additives may be pre-mixed into the thermoplastic resin to a concentration of 70 wt 2 or less, preferably 40 wt 2 or less to form a masterbatch, or kneaded to a working concentration to form a compound or during molding. Added in powder or liquid form.

In the present invention, in addition to additives other than those mentioned above, the thermoplastic resin may contain other additives, such as light-shielding substances, antistatic agents, colorants, antioxidants, lubricants, anti-fog agents, metal powders, and inorganic substances. , glass fiber, filler, and a coupling agent that performs molecular crosslinking at the interface between the filler and the polymer matrix to improve physical properties.

As the light-shielding substance, various carbon blacks, colored pigments, colored dyes, etc. can generally be used in an amount of 0.1 to 40% by weight.
As antistatic agents, quaternary ammonium salts, alanine type and diamine type amphoteric surfactant metal salts, imidacilline type amphoteric surfactant calcium salts, etc. are generally used in amounts of 0.1 to 5.
0 weight 2 can be used, and as lubricants, classified by chemical structure, hydrocarbon type (paraffin wax, fluorocarbon, etc.), fatty acid type, fatty acid amide type, alcohol type, metal soap, mixed type, etc. are generally 0.1 ~ 5.0 weight 2 can be used, and coupling agents (surface treatment agents) such as silane coupling agents, titanate coupling agents, chromium coupling agents, aluminum coupling agents, etc. are generally used at a weight of 0.2 to the filler. ~10 weight 2 can be used.

A thermoplastic material having the composition as described above is injection molded into a film case having a predetermined shape by an injection molding method.

FIG. 1 is a schematic diagram showing one embodiment of a movie film case made from the photosensitive material packaging material according to the present invention, and FIG.
This figure is a partial schematic diagram showing an engagement locking portion between the main body and the lid of the movie film case shown in FIG. 1.

This embodiment consists of a main body 2 made of a plastic light-shielding member with a cylindrical storage part L for storing an unexposed movie film wound on a reel, and a storage area for the main body 2. It consists of a lid 3 molded from a light-shielding member made of plastic, which has a cylindrical portion 3a which is fitted over and engaged with the portion 1 to shield and seal the film. The main body 2 has four engaging convex portions 5a, 5b, 5c, and 5d of the same cross-shaped shape, which are made of an outer wall surface and a clay wall surface, and extend along the wall surface 4 on the outside of the peripheral wall surface 4 of the storage section 1. is installed. These engaging protrusions 5a, 5b, 5c, and 5d are arranged at equal distances from the wall surface 4 and at the same intervals, and locking engaging recesses 8a, 8b, Be, has 8d. Note that the height of the peripheral wall surface 4 of the storage section 1 is desirably approximately the same as the thickness of the reel stored in the storage section 1 in order to ensure light-shielding properties. Furthermore, it is desirable that the inner diameter of the storage section 1 is large enough to accommodate the reel almost densely, but if a locking section for fixing the reel is provided inside the storage section 1, the inner diameter of the reel can be larger than the diameter of the reel. It's okay even if it is.

The lid body 3 includes an engaging convex portion 5a provided on the main body 2.

Four engaging holes 7a, 7b, 7c, ? with the same shape corresponding to 5b, 5c, 5d? d are provided, and these engagement holes 7a, 7b, ? c.? d are provided with approximately rectangular special notes 8a, 8b, 8c, and 8d that engage with the engaging convex portions 5a, 5b; 5c, and 5d. Further, adjacent to one of the retaining holes 7a, there is provided a lock pawl release pushing part 10 made of an elastic member and having a tapered lock pawl 8 in part. Note that after covering the top and side surfaces of the main body 2 with the lid 3,
1 body 2 so that it can be rotated relative to body 2
The four corners of the lid body 3 are formed into curved surfaces. In addition, when storing the film, the inside of the storage section 1 can be sealed and moisture-proofed by pasting a sealing material made of circular styrofoam or the like on the inner wall surface of the lid 3 so as to come into contact with the upper surface of the peripheral wall of the storage section l of the main body 2. desirable.

Next, operations when storing and removing the film will be explained.

When storing the film, store the reel on which the film is wound in the storage part l, and insert the reel into the engaging hole. a, 7b, 7c, 7d engaging convex insertion portion 11a, llb, lie, lid
The lid 3 is placed over the main body 2 so that the engaging protrusions 5a, 5b, 5c, and 5d are inserted. Thereafter, the lid 3 is rotated counterclockwise with respect to the main body 2 when viewed from above the lid. By this rotational operation, engagement hole protrusions 8a, 8b, 8c, and
8d is inserted substantially tightly, and at the same time, the lock claw 8 is pressed toward the outside of the lid 3 by the side wall 12 of the locking projection inserted into the engagement hole 11a. Roughly rotated engaging protrusions 5a, 5
b, 5c, 5d are engagement holes 11a, llb, ll
c. When the locking pawl 9 comes into contact with the circumferential edge of the lid, the locking pawl 9 engages with the four locking parts of the engagement protrusion, thereby preventing the engagement protrusion from moving in the rotational direction. FIG. 2 is a schematic diagram showing the arrangement of the engagement projection, the projection of the engagement hole, and the lock claw at this time.

In this way, the lid 3 and the main body 2 can be completely engaged and locked with one extremely simple operation, and the film stored inside can be sealed from light. There is no risk of accidents such as detachment from the film and exposure of the film.

Furthermore, when taking out the film, the lock release pusher lO
By pressing down with your finger to elastically deform the operation part itself and move the lock claw 9 toward the outside of the lid 3, the engagement protrusion is disengaged from the four locking parts 6, and at the same time, the lid 3
Rotate clockwise relative to the main body 2 when viewed from above the lid body, and remove the respective engaging convex portions 5a, 5b, and 5c.

5d to each engagement convex insertion portion 11a, llb, lic,
Make it match the lid. Thereafter, the lid 3 is removed from the main body 2 and the reel wound with film is taken out from the storage recess 1. In this way, in the film case of this embodiment, the lid 3 can be opened by pressing down the lock release pusher 10 with your finger.
The engagement between the lid 3 and the main body 2 can be released by simply rotating the film with respect to the main body 2, and the film removal operation is simple. Also, engaging convex portions 5a, 5b.

5c, 5d and engagement hole? a.? b, 7c, ?
d are all formed in the same shape and at the same spacing, so it is convenient because there is no need to check the pair of the engagement protrusion and the engagement hole.

Examples of the present invention will be described below.

Example 1 Polypropylene (Mitsubishi Yuka MS830)
,,,,,,,? ? , 5 wtygBaSO, ,,,,
,,,,,,,,,,,,,,,20,Owt,$4
°.

Carbon black, 2.0 tX dimethyl polysiloxane (Shin-Etsu Chemical Acid KF-98),
, , , , , 0.5 wtX Titanate coupling agent (KR-TTS isopropyl Φ triisostearoyl titanate, manufactured by U.S. Petrochemicals) , , , ,
, , , , , , 0.5 wt$ In addition, the above Ba5Q4
The amount is equivalent to 400 g/171' (assuming the thickness is 2 mm) +1 After thoroughly kneading the material with the above composition, this material is
A plastic sheet having a thickness of 21 mm was produced by injection molding at a temperature of .degree.

Cover the ASA250 color film for cinematography with this plastic sheet, and set the wavelength 0.01 from the X-ray tube (80 KV, 10 mA) at a distance of 1 (10 cps) from the sheet.
The X-ray blocking properties of the plastic sheets were measured from the density of the film after irradiation with X-rays of ~100 A and 10 VA X-ray intensity. The measurement results are shown in FIG. The upper part of FIG. 3 shows the color film G calendar temperature, and the lower part of FIG. 3 shows the temperature value of the color film R layer.

1 Also, by injection molding from materials of the same composition,
A film case as shown in the figure was integrally molded.

Film case shown in Figures 1 and 2 (thickness 2n+m
), ASA250 movie film was actually placed in the case, and the X-ray blocking properties and light blocking properties of the case were measured. The measurement of X-ray blocking properties is the same as that of the plastic sheet described above, and to measure the light blocking properties, an unexposed movie film film is placed in the four cylindrical parts of the lid body 3, and the inner wall surface of the lid body 3 is measured. A circular rubber sealing material is pasted on the film, and after it is completely fitted and sealed, it is exposed to light for 2 hours and then developed, and the transmission density is 0 when the film is developed without being exposed to full heat. I compared the differences.

In addition, suitability for stacking the cases, ease of opening/sealing, and appearance were sensually evaluated. These results and the measurement results of the X-ray blocking properties and light blocking properties are shown in Table 1 together with the results of Example 1. In Table 1, the X-ray blocking performance data is obtained by subtracting the complete X-ray blocking level value from each of the measured values in Table 3.

2 Example 2 Polypropylene (Mitsubishi Yukabu [9830), 0. ,
,,,,,. 72.5 wt$ zinc powder (200 meters/
25. Owtl carbon black, 2.0 tX dimethyl polysiloxane (Shin-Etsu Chemical Acid KF-88)-9-,
,,,,0.5wt$The above amount of zinc powder is 50
Corresponds to 0g/m'.

A sheet and a case similar to those in Example 1 were prepared by injection molding a material having the composition shown in 2 above, and measurements were conducted under the same conditions. The measurement results are shown in Table 1.

Example 3 Polypropylene (Mitsubishi Yukabu N5630)
,,,,,,79.0 KentX tin powder (150 mesh),,,,,,18. OwtX carbon black,,
, , , , , , 2. OwtX dimethylpolysiloxane (Shin-Etsu Chemical Acid KF-98), 0.5wt
X Silane coupling agent (Shin-Etsu Chemical KR KBN603N
-β-(aminoethyl)-γ-aminopropyl,
, , , , , , 0.5 wt$ The above amount of tin powder corresponds to 380 g /m'.

The same sheet as in Example 1 is obtained by injection molding the material having the above composition.
and cases were created and measurements were conducted under the same conditions. The measurement results are shown in Table 1.

Comparative Example 1 Polypropylene (Mitsubishi Yukabu MS830)
, , , , , 57. Okentz titanium oxide -0,9,4
0, Owt% titanate coupling agent (KR-TTS isopropyl triisostearoyl titanate, manufactured by U.S. Petrochemicals)
,,,,,,0.5 wt$Carpon Black---
, , , , , 2, Owtχ dimethylpolysiloxane (
, Shin-Etsu Chemical Acid KF-98), , , , , 0.5w
tX The same sheet and case as in Example 1 were made by injection molding the material having the above composition, and measurements were performed under the same conditions. The results are shown in Table 1.

Comparative Example 2 Polypropylene (Mitsubishi Yuka MS830)
, , , , 57.5 wt% aluminum powder (20
0 mesh) , , , , , , , , , , 40.0 Kent 2.0 t% dimethylpolysiloxane (Shin-Etsu Chemical KF-98)
The same sheet and case as in Example 1 were prepared by injection molding a material having the following composition: The results are shown in Table 1.

As is clear from the results shown in Table 1, the sheets and film cases using the thermoplastic material according to the present invention are not inferior in light shielding and X-ray shielding properties compared to conventional metal cans. Moreover, it has excellent stackability, ease of opening and sealing, and excellent appearance.

5 Preferred embodiments of the present invention are listed below. However, the present invention is not limited to these.

(i) The photosensitive material packaging material described at the beginning, wherein the thermoplastic resin is a polyolefin resin, a polystyrene resin, or an ABS resin.

(i i) The polyolefin resin is various polyethylenes,
The material according to item (i) above, which is a copolymer of various polyethylenes, various polypropylenes or copolymers of various polypropylenes, or a mixture of these resins and other thermoplastic resins.

(iii) The polystyrene resin is various polystyrene,
The material of item (i) above is a copolymer of various polystyrenes or a mixture of these resins and other thermoplastic resins.

(iv) ABS resin is various ABS resin, various AB
The material of item (i) above is a copolymer of S resins or a mixture of these resins and other thermoplastic resins.

(v) The photosensitive material packaging described at the beginning where the barium compound is barium sulfate, barium sulfite, barium chloride, barium hydroxide, barium metaboronate (Ba(BO3)2), or barium titanate (BaTi04). Materials for use.

(vi) The photosensitive material packaging material described at the beginning, wherein the zinc compound is zinc oxide or complexed zinc.

(vii) The photosensitive material packaging material described at the beginning, wherein the tin compound is tin oxide or the like.

(M1ii) The photosensitive material packaging material described at the beginning, wherein the lead compound is lead oxide, graphite, or lead potassium silicate.

(ix) One or more of a light-shielding substance, a coupling agent (surface treatment agent), an antistatic agent, a coloring agent, an antioxidant, a lubricant, an antiblocking agent, a metal powder, an inorganic substance, and a glass fiber in a thermoplastic resin. Including the materials for packaging photosensitive materials described at the beginning.

(The manufacturing method of the above metal powder is The photosensitive material packaging material described at the beginning is granular in shape.

(xi) The barium compound, zinc powder, zinc compound, tin powder, tin compound, lead powder, or lead compound as a filler is a silane coupling agent, a titanate coupling agent, a chromium-based coupling agent, or an aluminum-based coupling agent. The surface-treated photosensitive material packaging material described at the beginning.

(xii) In the above section xi, the amount of each coupling agent added is 0.1 to 10% by weight, preferably 0.3 to 5% by weight, most preferably 0.5 to 3% by weight, based on each filler. Materials for packaging photosensitive materials described in .

(xiii) 0.05 to 3.0% by weight, preferably 0.05 to 3.0% by weight of dimethylpolysiloxane in the resin composition in the above item xii.
3 to 1.5% by weight2, most preferably 0.5 to 1.0% by weight2.

(xii) In the above-mentioned item
．． 1 to 10% by weight2, preferably 0.5 to 7% by weight2, most preferably 1 to 5% by weight.

The material for packaging photosensitive materials according to the present invention is not limited to the examples and drawings, but can be widely applied. In other words, in the embodiments and drawings, a movie film case was explained, but
The material of the present invention can also be applied to a 35ml 11 film cartridge cartridge case for amateurs, a case for microfilm, a case for printed photosensitive materials, a case for sheet-shaped X-ray film, a case for computer typesetting film, and a case for photographic paper.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing an embodiment of a movie film case made from the photosensitive material packaging material according to the present invention, and FIG.
The figure is a partial schematic diagram showing the retention lock part, and FIG. 3 is a diagram showing the results of measuring the X-ray blocking property. 1. Storage section 2. Main body 3. 5d, , , , , , ,
Engagement protrusions 8, 8a, 6b, 8c, Eid,...
,,,,locking recess 9 7a, 7b, ? c、7d、、、、、、、、、、
, engaging holes 8a, 8b, 8c, 8d,...
, , , , Engagement protrusion 9 , , , , , , , Lock pawl 10 . . . Lock release pusher part Applicant
Fuji Photo Film Co., Ltd. Agent Patent Attorney Asa Kato Michi0

Claims (1)

[Claims] A photosensitive material packaging material containing 50 to 1,800 g/rn'' of at least one of a barium compound, zinc or a zinc compound, tin or a tin compound, lead or a lead compound in a thermoplastic resin.