JPS627047A - Holder for cassette of photographic film - Google Patents

Abstract

PURPOSE:To improve the workability of a package and the transparent degree of the titled holder by forming the titled holder, using a specific propylene copolymer resin. CONSTITUTION:The titled holder consists of a propylene-alpha-olefin random copolymer having a molar ratio of a propylene unit and an other alpha-olefin unit of 95.5/4.5-97.5/2.5, and 0.1-1.0wt% lubricant and 0.01-2.0wt% nucleus forming agent on the weight basis of the prescribed copolymer. The compound resin is a molding material having the melt index (ASTMD-1238) of 15-80g/10min and the bending modulus of elasticity (ASTMD-790) of >=9,000kg/cm<2>, the notched Izod impact strength (ASTMD-256) of >=2.0kg.cm/cm at 20 deg.C, and the mean thickness of the surroundings wall of 0.5-1.3mm. Thus, the holder capable of easily producing and having the excellent packaging workability and the high transparent degree may be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a container body for a photographic film cartridge.

[Prior art]

Conventional photographic film z4) The main body for the Rohne container is made of high-density polyethylene resin with a melt flow index (MI) of around 10 IZlO and a homo-type resin that does not contain ethylene to ensure rigidity and prevent flaking and stringing during injection molding. Polypropylene resin or ethylene content 2
Block type or random type polypropylene resins before and after Morti were used. Since these have poor transparency, they are usually colored by adding pigments.

Furthermore, Japanese Patent No. 58-46413 discloses a container for a photographic film cartridge made of a thin metal sheet material.

[Problem that the invention seeks to solve]

However, in the case of conventional containers made of high-density polyethylene resin or polypropylene resin, which have an MI of around 10 F/10 minutes, the walls must be thick to check compressive strength, drop strength, etc. The injection molding cycle time for the main body was increased, which increased manufacturing costs. Furthermore, if the photographic film is stored in the container body and left at high temperatures for a long period of time, the temperature inside the container increases and the quality of the film deteriorates. In addition, due to the rise in temperature, not only the container body but also the polystyrene resin inside was deformed.

In addition, containers made of thin metal sheets are expensive, have poor container formability, and are very expensive, so they are hardly put into practical use.

[Means for solving problems]

The present invention solves these problems and provides a container body for photographic film Noctrone that is thin, easy to manufacture, has excellent packaging processability, is highly transparent, and has high commercial value. 1. Using polypropylene resin with random physical properties. It is characterized by n7'l-.

That is, in the present invention, the molar ratio of glopyrene units to other α-olefin units is from 95.5:4.5 to
97.5: Propylene-α-olefin random copolymer resin having a ratio of 2.5 to 0.1 to 1.0% by weight of a lubricant and 0.97.5% by weight of a lubricant. Mel) 7o (7F Tx (ASTMD-1238) containing 1 to 2.0% by weight of a nucleating agent) was 15 to 8011710 minutes, and the flexural modulus (ASTMD-2
56) is 9000 kg/crn” or more and 20℃
Notched Noah Izod impact strength (ASTM D
A container for a photographic film cartridge having an average thickness of 0.5 to 1.3 m on the peripheral wall, which is formed using a propylene random copolymer resin having -256) of 2.0 hours/-v'- or more. This is related to the main body.

The propylene random copolymer resin forming the container body is a copolymer resin of propylene and other α-olefins. Other α-olefins are ethylene or those having about 4 to 13 carbon atoms, preferably about 4 to 10 carbon atoms, and specifically, ethylene, butene-1,4-butene-
1, hexene-1,4-methylpentene-1, octene-1, decene-1, dodecene-1, octadecene-1, and the like. These are not limited to one type, and two or more types can be copolymerized.

The ratio of glopyrene units and other α-olefin units in the copolymer is 95.5:4.5 to 95.5:4.5 in molar ratio.
97.5: 2.5 is appropriate.

If the α-olefin content is less than 2.5 in the above ratio, the stiffness will increase but the impact strength will decrease, and the containers may collide with each other during the packaging process. If the main body is sealed with a polyethylene resin cap and dropped from a high place, cracks may occur.

In addition, transparency decreases, especially in homotype polypropylene resins that do not contain α-olefins (HAZ
(E is large) The container body is not fragile and has low resistance to falling from a high place, resulting in a container body with very low commercial value.

If the α-olefin content exceeds 4.5 in the above ratio, the rigidity will decrease and, for example, if the container body is left in a collection box for a large number of people, it will deform due to its own weight and the cap will The strength of the fit decreases, causing the cap to come off during the packaging process. In addition, not only does injection moldability deteriorate, but molding failures such as threads, r-) residues, and bottom sinks occur, reducing the product value. Furthermore, during transportation processes such as conveyors and pneumatic transportation, scratches occur on the container body due to contact with other containers or transportation equipment. The problem, however, is that it is very quiet and has very high friction, which can lead to problems such as the inability to transport it.

In order to use such a propylene-α-olefin random copolymer resin as a material for the container body for photographic film, it is necessary to further add a lubricant and a nucleating agent to the resin. Generally, when the amount of α-olefin other than propylene is 2.5 molt or more, the coefficient of static and dynamic friction increases, and the rigidity decreases, causing deformation. Moreover, not only are scratches likely to occur on the inner and outer surfaces of the container body, but also injection moldability is deteriorated, and molding cracks, stringiness, and dirt residues are more likely to occur. These problems have been solved by blending a well-balanced lubricant and nucleating agent that do not have a negative effect on the photographic material, making it thin, easy to manufacture, easy to package, and resistant to drops from high places. It is possible to provide a container body for a photographic film cartridge that is excellent in quality and transparency, and has excellent commercial value.

The purpose of using a lubricant is to minimize the following: In other words, a propylene-α-olefin random copolymer resin with a melt flow index of 1,511,710 minutes or more has poor lubricity between the resins, making it difficult to feed the resin from the hopper to the molding machine, and causing problems with photographic film/4. If the plastic container body for Torone is not spherical but cylindrical or rectangular in shape, it may be difficult to remove it from the mold (mold releasability) or if crystallization is insufficient immediately after molding, scratches may occur due to blocking between the plastic container bodies. It occurs. If the content of α-olefin copolymerized with propylene is increased to 4.6 mole or more, impact strength, drop strength, transparency, etc. will improve, but the above-mentioned problem is that the melt flow index is 1!
If the resin is used for more than M/10 minutes, it will be rather amplified.

These can be improved by adding lubricants.

The lubricant used in the present invention is one that does not adversely affect the photographic material. Furthermore, it is preferable to use an inexpensive and easily available lubricant that does not cause a problem in the transparency of the container, has excellent mold releasability during container molding, and does not corrode the mold. Typical types of lubricants include higher fatty acid-based, silicone-based, metal soap-based, aliphatic hydrocarbon group, and fatty acid amide-based.

Commercially available lubricants particularly preferred for the present invention are listed below.

Silicone lubricant; Various dimethylpolysiloxanes (Shin-Etsu Silicone ((E) product, Toshi Silicone ((R) product)) Oleic acid amide lubricant; Armosli 7'CP (Lion Akzo ((E) product), Neutron ( Nippon Fine Chemical ((E) product), Nitron 118 (Nippon Fine Chemical ((T) product), Amide 0 (Nitto Chemical ((Company) product), Alflo EIO (Nippon Oil & Fats Co., Ltd. product), Diamond 0-200 (Nippon Kasei Co., Ltd. product).

Erucic acid amide lubricants such as Diamit G-200 (Nippon Kasei (Tan) products); Amyl stearate lubricants such as Alflow P-10 (NOF (Tan) products); Alflo S-10 (Nippon Oil & Fats ((Tan) products) Bis-fatty acid amide lubricants such as Nippon Fine Chemical Co., Ltd. products), 2, -Tron 2 (Nippon Fine Chemical Co., Ltd. products), Diamond 200 (Nippon Kasei Co., Ltd. products), etc.; Bisamide (Nippon Kasei Co., Ltd. products), Diamond 200 Bis (Nippon Kasei Co., Ltd. product), Armowax-EBS (Lion Akzo (
lead products), etc.

It is essential that the amount of the lubricant added be 0.1 to 1.0% by weight. If it is less than 0.1%, it is difficult to solve the above problems and it is impossible to put it into practical use as a container body for photographic film, page 4. On the other hand, if the weight exceeds 1.0, the screen will slip, and the surface of the container for photographic film cartridges will increase in stickiness, resulting in foreign matter adhesion and transfer to the photographic film. This will reduce the product value, etc. occurs. Moreover, the transparency of the container body is also reduced.

The propylene random copolymer resin has a melt flow index (ASTM D-1238) of 15 to
:18 Vl 0 min, preferably 20-60.
9/10 minutes, particularly preferably 30 to 50.9710 minutes, and a flexural modulus (ASTMD-790) of 9.9710 minutes. OO0
kg7cm” or more, preferably 13.OOOOkll/c
m” or more, and the notched Izot impact strength (ASTM D256) at 20°C is 2.0 kg・~
- and above. Furthermore, transparency (HAZE:ASTMD-1003
(measured value of a sheet having a thickness of 1 dew) is preferably 60% or less, particularly 40% or less.

A resin having such physical properties can be obtained by adding an appropriate amount of an organic or inorganic nucleating agent to the propylene random copolymer resin, which is the second additive essential to the present invention. be able to.

Organic nucleating agents include carboxylic acids, dicarganic acids, their salts and anhydrides, aromatic sulfonic acid salts and esters, aromatic phosphinic acids, aromatic phosphonic acids, aromatic carboxylic acids, their aluminum salts, aromatic Group metal phosphate, carbon number 8
~30 alkyl alcohols, condensates of polyhydric alcohols and aldehydes, and alkylamines, such as aluminum pt-butylbenzoate, 1,3,2
．． 4-dibenzylidene sorbitol, a di-substituted pennolidene sorbitol compound represented by the following formula (wherein R1 and R2 are alkyl, alkoxy or halodane having 1 to 8 carbon atoms and 6t), m and n are both 0 to
3, and m-1-n≧1. ), gold M[, N-(
Compounds represented by the following formula such as 2-hydroxyethyl)-stearylamine (wherein R3 is an alkyl group having 8 to 30 carbon atoms, and k and t are both 0 to 10 and -)- Al if 2≧1. ), metal salts of 1.2-hydroxystearic acid such as lithium salts, sodium salts, potassium salts, calcium salts, and magnesium salts, alkyl alcohols such as stearyl alcohol and lacryl alcohol,
Contains benzoic acid, benzoic acid, sepatenoic acid, etc.

Inorganic nucleating agents include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, alkali metal oxides such as sodium oxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate. alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide, barium hydroxide, and alkaline earth metal oxides such as calcium carbonate and calcium oxide.

The nucleating agent is not limited to these, and other known nucleating agents can also be used. Moreover, it goes without saying that the nucleating agent is not limited to being used alone, and that two or more types can be used in combination.

The amount of the nucleating agent added is 0.01 to 2.0 parts by weight per 100 parts by weight of the propylene-α-olefin/random copolymer resin.

The nucleating agent can be added to the propylene-α-olefin random copolymer resin by the general method of adding various additives to polypropylene, etc., and usually it is added to the propylene random copolymer resin uniformly. All you have to do is knead it.

Various effects can be obtained by adding this nucleating agent. Example Eva, propylene-α-olefin random copolymer resin as propylene and ethylene random copolymer resin 1
By adding 0.1 part by weight of paratertiary butylbenzoic acid as a nucleating agent to 00 parts by weight, HkZE can be reduced from 40 to 21 parts, and by adding 0.2 parts by weight, it can be further reduced to 12%. be able to. The yield point stress is, for example, 380 k417 when 0.1 part by weight is added.
cm'' to 420 kliI/cm'', but even if it is added beyond that, there is almost no improvement after that. Further, when 0.1 part by weight is added, the flexural modulus can be improved from, for example, 500 ψ et al 2 to 600 ψ j 2 , but even if more than that is added, there is little improvement thereafter.

In addition to the above-mentioned lubricant and nucleating agent, various additives can be added to the propylene random copolymer resin used for the container body of the present invention. Representative examples of known additives are shown below.

(Additive types) (Typical examples) (1) Plasticizers: phthalate esters, glycol esters, fatty acid esters, phosphate esters, etc. (2) Stabilizers: lead-based, cadmium-based, zinc-based, alkaline earth metal-based, Organotin-based etc. (3) Antistatic agent; cationic activator, anionic activator,
Nonionic activators, bifacial activators, etc. (4) Flame retardants; phosphoric acid esters, norodunated phosphoric esters, halides, inorganic substances, phosphorous-containing polyols, etc. (5) Fillers: alumina, kaolin, clay, calcium carbonate, mica, talc , titanium oxide, silica, etc. (6) Reinforcing agents; glass roving, metal fibers, glass fibers, glass milled fibers, carbon fibers, etc. (7) Coloring agents: Inorganic pigments (At, Fe2O2, TiO□
, ZnO, CdB.

(8) Vulcanizing agents; Vulcanization accelerators, accelerators, etc. (9) Deterioration inhibitors; Ultraviolet absorbers, antioxidants agents, metal deactivators, peroxide decomposers, etc. (10) Coupling agents; silane-based, titanate-based, chromium-based, aluminum-based, etc. α various thermoplastic resins, rubber, etc. (2) Other containers of the present invention The shape of the main body is not particularly limited as long as it can accommodate a photographic film cartridge;
It is preferable to have a cap that exhibits sufficient fitting and sealing properties with the cap and that allows for easy attachment and detachment of the cap, and in this respect, for example, the examples shown in FIG. 1 and FIG. 2 are suitable. In particular, the one shown in FIG. 1 has the advantage of being easy to open with one hand. The wall thickness of the container body 1 can be made thinner than conventional products, for example, the wall thickness of the peripheral wall portion 2 is 0.5 to 1.3 square inches, preferably 0.7 to 1.0 square inch.
The degree is appropriate. The material of the cap 3 is different from that of the container body 1 in order to fully utilize these functions of the container body 1.
A material that is very flexible is preferred, such as low density/IJ ethylene low pressure linear low density polyethylene (L-LDPE). The container body may normally be manufactured by injection molding. The injection molding method is not particularly limited, and for example, an in-mold nitrogen injection molding method may be used.

It is more efficient to use a mold that can mold a large number of containers, for example, one that can mold 12 or more container bodies at once, rather than one mold.

In the case of injection molding, as shown in FIGS. 1 and 2, from the point where the resin protrusion 5 remains in the resin injection port 4,
This resin injection port 4 is approximately 0.5 to 5 wm from the bottom surface 6.
Preferably, it is provided with a recess of about 1 to 3 cm, but the present inventors have found that pinholes are likely to occur in this portion 4, particularly when manufacturing the container body 1 of the present invention. Kon
In order to avoid this, it is preferable that the area around the resin injection port 4 be thicker than the average thickness of the bottom 7 as shown in the figure. This is particularly important when the thickness of the container body 1 is made thin, for example, 0.7 gourd or less.

The method of molding the container body is not limited to injection molding, but may be molded by injector 1 blow molding or blow molding if necessary.

Generally, a film Hatrone container is commercialized by being stored in a paper box as an outer box along with a film usage manual, but since the container body of the present invention is also characterized by transparency, By making the outer box double as a
It is possible to further demonstrate its characteristics and reduce costs at the same time. Examples of container bodies used for such purposes are shown in FIGS. 3 to 5. FIG. 3 shows an example of a cylindrical shape, FIG. 4 shows an example of a rectangular cylinder shape, and FIG. 5 shows an example of a square outer shape with a circular storage portion.

[Effect]

In the present invention, a polypropylene resin which has excellent rigidity and is suitable as a material for the container body has been subjected to various improvements, thereby completing a container body for photographic film torone having a number of excellent properties. In other words, by adding an appropriate amount of other α-olefins to propylene to form a copolymer, impact strength is greatly improved, rigidity is adjusted to an appropriate range, and transparency is also improved. The increase in the coefficient of friction caused by the addition of this α-olefin is suppressed by adding an appropriate amount of lubricant. Furthermore, even if the melt 70-index is increased by adding an appropriate amount of a nucleating agent, the flexural modulus, Izod impact strength, etc. are improved to provide desirable physical properties, and the transparency is further improved.

〔Example〕

Using Sumitomo Heavy Industries' Nestal (trade name) as a molding machine,
Mold squeezing pressure 1501. The number of holes is 24, and the liner type is a hot liner with the shape shown in Figure 1, and the side wall thickness is 0.8-
The bottom shape of the /9 Torone container body was made.

The conventional product ■ is a propylene ethylene random copolymer resin with a propylene unit content of 98 moles and an ethylene content of just 2 moles, a melt flow index of 12.0,9710 minutes, and a flexural modulus of 11. 000'
Q/cm", the notched isot impact strength at 20°C is 3.5 kg・Cjn/Cm, and the random type polypropylene resin contains 0.2% by weight of oleic acid amide as a lubricant and does not contain a nucleating agent. Using.

As a conventional product■, the melt flow index is 10#
/10 minutes homotype I polypropylene resin container body was used.

Comparison field 1 is a propylene-based random copolymer resin with a propylene content of 96 moles and an ethylene content of 4 moles, with a Simelt 70-index of 25.97.
10 minutes, flexural modulus 9,200 kg7cm”, 20℃
Notched Izot impact strength is 4.0 kg
- A random type polypropylene resin containing no lubricant or nucleating agent was used.

Comparison field 2 is made of a propylene ethylene random copolymer resin with a propylene unit content of 98 moles and an ethylene content of 2 moles, a melt flow index of 40.0 J710 minutes, and a flexural modulus of 1,000 kll/c.
Random type polypropylene resin having a notched Izo impact strength at 20°C of 5.0 kg・-/3, containing 0.3% by weight of oleic acid amide as a lubricant, and 0.1% by weight of a nucleating agent. was used.

Inventive product 1 is a propylene ethylene random copolymer resin with a propylene content of 97 moles and an ethylene content of 3 moles, and a melt flow index of 4.
0.011/10 min, flexural modulus 14.000 kl/c
m”, the notched Izo impact strength at 20°C is 6.0 kg・crti 7 cm, and the random type contains 0.3 weight % of oleic acid amide as a lubricant and 0.1% by weight of a nucleating agent. Polypropylene resin was used.

Inventive product 2 is a propylene-ethylene random copolymer resin with a propylene content of 96 moles, an ethylene content of just a few moles, and a melt flow index of 40.
．． 0. F710 minutes, bending elastic modulus 11000 Yu/c! R2
, notched Izo impact strength at 20°C is 5.
A random type polypropylene resin having a weight of 0 k8g·cm/crs and containing 0.5% by weight of oleic acid amide as a lubricant and 0.1% by weight of a nucleating agent was used.

These 6 kinds of photographic films aJ? ) Table 1 shows the results of comparing the characteristics of the Rohne container body using the following evaluation method.

Although the above examples are representative examples of preferred embodiments of the photographic film/arm trone container body of the present invention, the present invention is not limited thereto.

The evaluation in the table is based on the following.

○Very good ○ExcellentΔPractical limit MU Somewhat problematic (improvement required) × Not practical The tests in the table are as follows.

Incidence of cracking when falling from 15m; 5m after taking 36-shot photo film (Fujicolor HR-10036EX) and sealing with n cap.
The probability of cracking when falling from a height of 100 to a concrete floor.

*2 Transparency: Draw parallel lines on a blank sheet of paper with a line thickness of 0.5 m, and then place the container body between the eyes and the transparency inspection paper on the back of the container body. Transparency is defined as the distance (3) at which the parallel lines above become invisible.

*3 Compressive strength: The maximum force required to apply pressure to the container body with a flat plate and deform it is the compressive strength.

*4 Degree of fit: Attach the cap to the tip of the spring scale and measure the force required to remove the cap by pulling it straight up.*5 Degree of wear on the inner wall of the container body: Arm Torone photographic film When the film is rotated and inserted into the container body, the inner wall is worn and the amount of white powder that adheres to the photographic film is visually inspected.

*6 Sliding between containers 5 minutes after forming: Stack the container bodies 5 minutes after forming in bales on a plate, increase the angle of the plate, and measure at the angle at which the container bodies begin to slide. The higher the value, the harder it is to slip.

*7 Bottom sink: Put ink on the bottom of the container body, press it on a blank sheet of paper like a stamp, and visually observe and evaluate the pressed shape.

*8 Incidence of seals: degree of insufficient resin filling when 10,000 pieces are injection molded *9 Efficiency of product quantity: photographic film mother trone is placed in a plastic container body fixed to a board. Insert the photographic film at a larger angle and measure the angle at which the photographic film rolls out. Small values are preferred because they are easy to take out.

*10 threads; 50 threads) (1200 pieces) The extent to which long thread-like failures occur at the resin inlet mark during injection molding *11 Molding cycle; 1 shot time from injection to cooling to removal [Invention [Effects] The main body for the photographic film/4-troinette container of the present invention has a high Izotsu impact strength, and as a result, has a very high drop strength (very low cracking rate when dropped from 5 m). Even during logistics engineering, cracks tend to occur in the container body. Furthermore, the fitting strength and fitting sealability with the cap are good.

Even though the drop impact strength was greatly improved by increasing the ethylene (including α-olefin) content, the compressive strength and abrasion resistance of the inner wall of the container body did not deteriorate. During molding, not only is the molding shrinkage rate low and the dimensional stability is good, but there are also few occurrences of threads and scratches, and the product is easy to take out.

It has good moldability, and has good releasability between the mold and container and good lubricity immediately after molding.

Since the resin has good fluidity, there are fewer short-sits and bottom sinks, which shortens the molding cycle and reduces the number of defective products.

Due to the above characteristics, a predetermined strength can be ensured even if the container body is made thin, and the transparency of the container body can be greatly improved, thereby achieving cost reduction while increasing the product value.

By making the container body double as the outer box, it is possible to reduce costs, add novelty to the product, and furthermore give the consumer a sense of security as they can confirm the contents. It is also effective to print on the outside to improve the product value or add explanatory text.

The container body for a photographic film Noctrone according to the present invention does not need to be transparent, and may be used as a container body for a photographic film cartridge made translucent or opaque by adding metal powder, pigments, or dyes. The container body for the transparent photographic film Nojatrone has been further improved and is much superior to conventional products.

[Brief explanation of drawings]

Each of the drawings represents an embodiment of the present invention, and FIGS. 1 and 2 are cross-sectional views of the container body and the cap. 3 to 5 are perspective views of an example in which the outer box is also used. DESCRIPTION OF SYMBOLS 1... Container main body, 2... Surrounding wall part, 3... Cap, 4... Resin injection port part, 5... Resin injection port (f-)
) marks, 6...bottom surface, 7...bottom Patent applicant Fuji Photo Film Co., Ltd. Agent
Patent Attorney 1) Masa Hiroshi Naka 1st! f Figure 2

Claims (2)

[Claims] (1) The ratio of propylene units to other α-olefin units in terms of mol% is 95.5:4.5 to 97.5:2.5
The melt flow index (ASTM D- 1238) is 15-80g/10 minutes, flexural modulus (ASTM D-790) is 9000kg
/cm^2 or more, and the notched Izod impact strength (ASTM D-256) at 20℃ is 2.0kg
・The average thickness of the peripheral wall is 0.5 to 0.5 cm/cm or more and is formed using a propylene random copolymer resin.
Container body for 1.3mm photographic film cartridge (2) HAZE of propylene random copolymer resin (
The container body for a photographic film cartridge according to claim 1, which has a film thickness of 60% or less (measured value of a 1 mm thick sheet according to ASTM D-1003)